Catalyst Composition Comprising Fluorided Support and Processes for Use Thereof

ABSTRACT

This invention relates to a catalyst system comprising fluorided silica, alkylalumoxane activator and at least two metallocene catalyst compounds, where the first metallocene is a bridged monocyclopentadienyl group 4 transition metal compound and the second metallocene is a biscyclopentadientyl group 4 transition metal compound, where the fluorided support has not been calcined at a temperature of 400° C. or more, and is preferably produced using a west mixing method, such as an aqueous method.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a National Phase Application claiming priority to PCT Application Serial No. PCT/US2016/021748 filed Mar. 10, 2016, and claims priority to and the benefit of U.S. application Ser. No. 62/149,799, filed Apr. 20, 2015 and EP Application No. 15172225.3, filed Jun. 16, 2015, the disclosures of which are hereby incorporated by reference in their entireties.

FIELD OF THE INVENTION

This invention relates to novel catalyst compositions comprising a monocyclopentadienyl transition metal compound, a biscyclopentadientyl transition metal compound, a flourided support, and an optional activator and uses thereof.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hence, there is interest in finding new catalyst systems that increase the commercial usefulness of the catalyst and allow the production of polymers having improved properties.

Catalysts for olefin polymerization are often based on cyclopentadienyl transition metal compounds as catalyst precursors, which are activated either with an alumoxane or with an activator containing a non-coordinating anion.

A typical metallocene catalyst system includes a metallocene catalyst, a support, and an activator. Supported catalyst systems are used in many polymerization processes, often in slurry or gas phase polymerization processes. For example, U.S. Pat. No. 6,846,770 and U.S. Pat. No. 6,664,348 disclose catalyst compositions containing at least one metallocene, and least one activator and a support that has been flourided using a fluoride containing compound and their use in the Examples to make polypropylene in a slurry process. U.S. Pat. No. 6,846,770 and U.S. Pat. No. 6,664,348 do not address a particular combination of metallocenes and flourided support where the first metallocene is a monocyclopentadienyl transition metal compound and the second metallocene is a biscyclopentadientyl transition metal compound.

WO 05/075525 describes supports for metallocene catalyst systems of inorganic oxides treated with a fluorinated functionalizing agent, for example, diethyl aluminium fluoride.

U.S. Publication No. 2002/007023 describes alumina supports treated with ammonium bifluoride or perfluorohexane which are used with metallocenes and organoalumimum compounds for the polymerization of olefins.

WO 2003/025027 describes fluorided metal oxides as supports for phosphinimine/aluminoxane polymerization catalyst systems.

U.S. Publication No. 2005/0288461 describes fluorided silica/alumina supports for metallocene/organoaluminium catalyst systems. The supports are pretreated, for example, with ammonium bifluoride.

U.S. Publication No. 2014/0031504 discloses examples of dimethylaluminium fluoride treated silica combined with activator of [N(H)Me(C₁₈₋₂₂H₃₇₋₄₅)₂][B(C₆F₅)₃p-OHC₆H₄)] and catalyst compound of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) to copolymerize ethylene and hexene.

Metallocenes are often combined with other catalysts, or even other metallocenes, to attempt to modify polymer properties. For example, U.S. Pat. No. 8,088,867 discloses a polymer blend prepared by the process of combining under solution polymerization conditions: (A) a first catalyst capable of producing a first crystalline polymer having an Mw of 100,000 or less, (B) a second catalyst capable of preparing a second amorphous polymer having an Mw of 100,000 or less and differing in chemical or physical properties from the first polymer under equivalent polymerization conditions, (C) a cocatalyst, activator, scavenger, or combination thereof, and (D) one or more olefins; wherein the polymer blend is formed in-situ, comprises crystalline polymer segments and amorphous polymer segments, and has an Mw of 100,000 or less. The examples at column 98, line 18 et seq. state:

“The catalyst compounds used to produce semi-crystalline polypropylene were rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl, rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl, rac-dimethylsilylbis(indenyl)hafnium dimethyl, and rac-1,2-ethylene-bis(4,7-dimethylindenyl)hafnium dimethyl . . . . The catalyst compounds used to produce amorphous polypropylene were dimethylsilyl(tetramethylcyclopentadienyl) (cyclododecylamido)titanium dichloride, dimethylsilyl(tetramethylcyclopentadienyl) (cyclododecylamido)titanium dimethyl, dimethylsilyl(tert-butylamino) (tetramethylcyclopentadienyl)titanium dimethyl . . . .”

Likewise, U.S. Pat. No. 5,516,848 discloses the use of two different cyclopentadienyl based transition metal compounds activated with alumoxane or non-coordinating anions. In particular, the examples disclose, among other things, catalyst compounds in combination, such as Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂ and rac-Me₂Si(H₄Ind)ZrCl_(2,) or Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂ and Me₂Si(Ind₂)HfMe₂, (Ind=indenyl) activated with activators such as methyl alumoxane or N,N-dimethyl anilinium tetrakis(pentafluorphenyl)borate to produce polypropylenes having bimodal molecular weight distributions (Mw/Mn), varying amounts of isotacticity (from 12 to 52 weight % isotactic PP in the product in Ex 2, 3 and 4), and having weight average molecular weights over 100,000, and some even as high as 1,200,000 for use as thermoplastics.

Likewise, two different catalysts have been placed on a support to make polyolefins, typically in gas phase. For example, U.S. Pat. No. 4,701,432 and U.S. Pat. No. 5,077,255 relate to olefin polymerization catalyst compositions comprising a metallocene and anon-metallocene impregnated on a support. Further, U.S. Pat. No. 7,141,632 describes supported two catalyst systems used gas phase to produce ethylene hexene copolymers. U.S. Pat. No. 6,207,606 also describes supported dual metallocene catalyst systems useful in gas phase polymerizations.

U.S. Pat. No. 8,598,061, at Examples 7-10 discloses two bis-cyclopentadienyl metallocenes on a fluorided silica-alumina.

Hong et al. in Immobilized Me ₂ Si(C ₅ Me ₄)(N-t-Bu)TiCl ₂/(nBuCp)₂ ZrCl ₂ Hybrid Metallocene Catalyst System for the Production of Poly (ethylene-co-hexene) with Psuedo-bimodal Molecular Weight and Inverse Comonomer Distribution, (Polymer Engineering and Science-2007, DOI 10.1002/pen, pages 131-139, published online in Wiley InterScience (www.interscience.wiley.com) 2007 Society of Plastics Engineers), disclose (C₅Me₄)(N-t-Bu)TiCl₂/(nBuCp)₂ZrCl₂ supported on silica used to make ethylene-hexene copolymers where the polymerization rate drops over a short time.

U.S. Publication No. 2012/0130032 discloses a supported monocyclopentadienyl catalyst composition (e.g., SiMe₂(C₅Me₄)(NtBu)Ti eta-4-1,3-pentadiene) for use in gas phase polymerization to make ethylene hexene copolymers.

U.S. Pat. No. 7,192,902 at example 6 discloses preparation of polypropylene using SiMe₂(C₅Me₄)(NtBu)TiCl₂/MAO and SiMe₂(2-Me-4-Ph-indenyl)₂ZrMe₂/trisperfluorophenylboron on a silica support. Example 3 discloses silica support treated with ammonium hexafluorosilicate and calcined at 500° C. The catalysts appear to be activated in sequence.

U.S. Pat. No. 8,110,518, discloses preparation of various fluorided silica or silica-alumina supports, which are eventually used for propylene (co)polymerization with various biscyclopentadienyl transition metal compounds. Also, U.S. Pat. No. 8,110,518 discloses preparation of fluorided silica-alumina support in a water slurry with NH₄F.HF.

Activators useful in metallocene polymerization have also been modified in an attempt to improve the catalyst systems. For example U.S. Pat. No. 7,355,058 discloses catalysts containing haloaluminoxane compositions, where the halogen is fluorine, chlorine, and/or bromine, and is present at about 0.5 mole % to about 15 mole % relative to aluminum atoms.

Other references of interest include: U.S. Pat. No. 5,382,630; U.S. Pat. No. 5,382,631; U.S. Pat. No. 8,575,284, U.S. Pat. No. 6,069,213; Kim, J. D. et al., J. Polym. Sci. Part A: Polym Chem., 38, 1427 (2000); Iedema, P. D. et al., Ind. Eng. Chem. Res., 43, 36 (2004); U.S. Pat. No. 6,656,866; U.S. Pat. No. 8,815,357; U.S. Publication No. 2014/0031504; U.S. Pat. No. 5,135,526; U.S. Pat. No. 7,385,015; WO 2007/080365; WO 2012/006272; WO 2014/0242314; WO 00/12565; WO 02/060957; and WO 2004/046214.

There is still a need in the art for new and improved catalyst systems for the polymerization of olefins, in order to achieve increased activity or specific polymer properties, such as high melting point, high molecular weights, to increase conversion or comonomer incorporation, or to alter comonomer distribution without deteriorating the resulting polymer's properties.

It is therefore also an object of the present invention to provide novel supported catalysts systems and processes for the polymerization of olefins using such catalyst systems.

The supported multiple-metallocene catalyst systems described herein address these needs by producing multimodal polyethylene containing an ultra-high Mw (greater than 1,000,000 g/mol), high short-chain branching (SCB) component, that when formed into a film has improved properties (such as toughness, stiffness and or processability).

SUMMARY OF THE INVENTION

This invention relates to a catalyst system comprising fluorided silica, alkylalumoxane activator and at least two metallocene catalyst compounds, where the first metallocene is a bridged monocyclopentadienyl group 4 transition metal compound and the second metallocene is a biscyclopentadientyl group 4 transition metal compound, where the fluorided support has not been calcined at a temperature of 400° C. or more.

This invention also relates to a process to produce ethylene polymer comprising: i) contacting, in the gas phase or slurry phase, ethylene and C₃ to C₂₀ comonomer with a catalyst system comprising a flourided support, an alkyl alumoxane activator, and at least two metallocene catalyst compounds, where the first metallocene is a bridged monocyclopentadienyl group 4 transition metal compound and the second metallocene is a biscyclopentadientyl group 4 transition metal compound, where the flourided support has not been calcined at a temperature of 400° C. or more, and ii) obtaining a polymer comprising at least 50 mol % ethylene.

This invention also relates to a catalyst system comprising a flourided support, an alkylalumoxaneactivator, and at least two metallocene catalyst compounds, where the metallocenes are represented by the formula:

T_(y)Cp_(m)MG_(n)X_(q)

wherein each Cp is, independently, a cyclopentadienyl group (such as cyclopentadiene, indene or fluorene) which may be substituted or unsubstituted, M is a group 4 transition metal, for example, titanium, zirconium, hafnium, G is a heteroatom group represented by the formula JR*_(z) where J is N, P, O or S, and R* is a C₁ to C₂₀ hydrocarbyl group and z is 1 or 2, T is a bridging group, and y is 0 or 1, X is a leaving group (such as a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group), and m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal; wherein m=1, n=1 and y=1 in the first metallocene catalyst compound; and n=0 and m=2 in the second metallocene catalyst compound, provided that when y=1 in the second metallocene compound, then at least one Cp is preferably not an indene group.

This invention also relates to metallocene catalyst compositions comprising the reaction product of at least four components: (1) one or more bridged metallocenes having one cyclopentadienyl ring; (2) one or more metallocenes having two cyclopentadienyl rings; (3) one or more alkylalumoxaneactivators; and (4) one or more flourided support compositions, where the flourided support composition has not been calcined at 400° C. or more.

This invention further relates to polymer compositions produced by the methods described herein.

This invention also relates to a method of preparing flourided supported catalyst systems comprising combining a fluoride compound with polar solvent, then combining with a slurry of non-polar solvent and support, removing the non-polar solvent, then calcining the support at less than 400° C., thereafter combining the calcined support with solvent and two catalyst compounds and activator, wherein the flourided support may be calcined at a temperature from 100 to less than 400° C., before or after combination with the activator and/or catalyst compounds.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1a is the GPC-3D graph for PE produced with supported catalyst a-1.

FIG. 1b is the GPC-IR graph for PE produced with supported catalyst a-1.

FIG. 2a is the GPC-3D graph for PE produced with supported catalyst b-1.

FIG. 2b is the GPC-IR graph for PE produced with supported catalyst b-1.

FIG. 3a is the GPC-3D graph for PE produced with supported catalyst c-1.

FIG. 3b is the GPC-IR graph for PE produced with supported catalyst c-1.

FIG. 4 is the GPC-3D graph for PE produced with supported catalyst d-1.

FIG. 5a is the GPC-3D graph for PE produced with supported catalyst e-1.

FIG. 5b is the GPC-4D graph for PE produced with supported catalyst e-1.

FIG. 5c is the TREF of PE produced from supported catalyst e-1.

FIG. 6a is the GPC-4D of PE produced with supported catalyst f-1.

FIG. 6b is the TREF of PE produced with supported catalyst f-1.

FIG. 6c is the CFC graph for PE produced with supported catalyst f-1.

FIG. 7 is the TREF of PE produced with supported catalyst g-2.

FIG. 8a is the TREF of PE produced with supported catalyst h-1.

FIG. 8b is the CFC of PE produced with supported catalyst h-1.

FIG. 9 is a proton NMR trace for four supports, from top to bottom: 1) reaction mixture of (NH₄)₂SiF₆ and MAO solution; 2) reaction mixture of silica-1 and MAO solution; 3) reaction mixture of silica-2 and MAO solution.

DETAILED DESCRIPTION

For the purposes of this invention and the claims thereto, the new numbering scheme for the Periodic Table Groups is used as described in CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985), e.g., a “Group 4 metal” is an element from Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35 wt % to 55 wt %, it is understood that the mer unit in the copolymer is derived fromethylene in the polymerization reaction and said derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mole % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mole % propylene derived units, and so on.

For the purposes of this invention, ethylene shall be considered an α-olefin.

For purposes of this invention and claims thereto, the term “substituted” means that a hydrogen group has been replaced with a heteroatom, or a heteroatom containing group. For example, a “substituted hydrocarbyl” is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom or heteroatom containing group.

As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt % is weight percent, and mol % is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity, is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol. The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, Bn is benzyl, Cp is cyclopentadienyl, Cp* is pentamethyl cyclopentadienyl, Ind is indenyl, Flu is fluorenyl, and MAO is methylalumoxane.

For purposes of this invention and the claims thereto, a “catalyst system” is the combination of at least two catalyst compounds, at least one activator, an optional co-activator, and flourided support material. For the purposes of this invention and the claims thereto, when catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.

In the description herein, the metallocene catalyst may be described as a catalyst precursor, a pre-catalyst compound, metallocene catalyst compound or a transition metal compound, and these terms are used interchangeably.

A metallocene catalyst is defined as an organometallic transition metal compound with at least one π-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two π-bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties bound to a transition metal.

For purposes of this invention and claims thereto in relation to metallocene catalyst compounds, the term “substituted” means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group. For example, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.

For purposes of this invention and claims thereto, “alkoxides” include those where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. In some embodiments, the alkyl group may comprise at least one aromatic group.

This invention relates to a catalyst system comprising a fluorided support, an alkylalumoxane activator, and at least two metallocene catalyst compounds, where the first metallocene is a bridged monocyclopentadienyl group 4 transition metal compound and the second metallocene is a biscyclopentadientyl group 4 transition metal compound, preferably the metallocenes are represented by the formula:

T_(y)Cp_(m)MG_(n)X_(q)

wherein Cp is a cyclopentadienyl group (such as cyclopentadiene, indene or fluorene) which may be substituted or unsubstituted, M is a group 4 transition metal, for example, titanium, zirconium, hafnium, G is a heteroatom group represented by the formula JR*_(z) where J is N, P, O or S, and R* is a C₁ to C₂₀ hydrocarbyl group and z is 1 or 2, T is a bridging group, and y is 0 or 1, X is a leaving group (such as a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group), and m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal (preferably 2, 3, 4, 5 or 6, preferably 4); wherein m=1, n=1 and y=1 in the first metallocene catalyst compound and n=0 and m=2 in the second metallocene catalyst compound, provided that when y=1 in the second metallocene compound, then at least one Cp is preferably not an indene group.

Generally, two or more different catalyst compounds are present in the catalyst system used herein. When two transition metal compound based catalysts are used as a mixed catalyst system, the two transition metal compounds are preferably chosen such that the two are compatible. A simple screening method such as by ¹H or ¹³C NMR, known to those of ordinary skill in the art, can be used to determine which transition metal compounds are compatible. It is preferable to use the same activator for the transition metal compounds, however, two different activators, such as anon-coordinating anion activator and an alumoxane can be used in combination. If one or more transition metal compounds contain an X₁ or X₂ ligand which is not a hydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane may be contacted with the transition metal compounds prior to addition of the non-coordinating anion activator.

The two transition metal compounds (pre-catalysts) may be used in any ratio. Preferred molar ratios of (A) monocyclopentadienyl transition metal compound to (B) biscyclopentadienyl transition metal compound fall within the range of (A:B) 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. The particular ratio chosen will depend on the exact pre-catalysts chosen, the method of activation, and the end product desired. In a particular embodiment, when using the two pre-catalysts, where both are activated with the same activator, useful mole percents, based upon the molecular weight of the pre-catalysts, are 10 to 99.9% A to 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50% B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99% A to 1 to 10% B.

The combined catalyst compounds are present on the support at 1 to 100 μmol/g supported catalyst, preferably 20-60 μmol/g supported catalyst.

This invention also relates to metallocene catalyst compositions comprising the reaction product of at least four components: (1) one or more bridged metallocenes having one cyclopentadienyl group; (2) one or more metallocenes having two or three cyclopentadienyl groups; (3) one or more alkylalumoxane activators; and (4) one or more fluorided support compositions, where the fluorided support composition has not been calcined at 400° C. or more, preferably the fluorided support composition has been calcined at a temperature of 100° C. to 395° C., alternately 125° C. to 350° C., alternately 150° C. to 300° C.).

Typically, the fluorided supports described herein are prepared by combining an aqueous solution of fluorinating agent (such as SiF₄ or (NH₄)₂SiF₆) with a slurry of support (such as a toluene slurry of silica), then drying until it is free flowing, and optionally, calcining (typically at temperatures over 100° C. for at least 1 hour). The supports are then combined with activator(s) and catalyst compounds (separately or together).

Fluorided Supports

As used herein, the phrases “fluorided support” and “fluorided support composition” mean a support, desirably particulate and porous, which has been treated with at least one inorganic fluorine containing compound. For example, the fluorided support composition can be a silicon dioxide support wherein a portion of the silica hydroxyl groups has been replaced with fluorine or fluorine containing compounds. Likewise, the term “support composition” means a support, desirably particulate and porous, which has been treated with at least one fluorine containing compound. Suitable fluorine containing compounds include, but are not limited to, inorganic fluorine containing compounds and/or organic fluorine containing compounds.

Supports suitable for use in this invention are generally porous materials and can include organic materials, inorganic materials and inorganic oxides. Desirably, supports suitable for use in this invention include talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thona, aluminum phosphate gel, polyvinylchlonde and substituted polystyrene and mixtures thereof. Other useful support materials include zeolites, clays, organoclays, or any other organic or inorganic support material and the like, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finely divided form. Suitable inorganic oxide materials for use in the catalyst systems described herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like. Other suitable support materials, however, can be employed, for example, finely divided functionalized poly olefins, such as finely divided polyethylene. Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like. Preferred support materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof, more preferably SiO₂, Al₂O_(3,) or SiO₂/Al₂O₃. In a preferred embodiment, of the invention, the support is silica.

It is preferred that the support material, preferably an inorganic oxide, preferably silica, has a surface area in the range of from about 10 to about 800 m²/g (alternately about 10 to about 700 m²/g), pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 μm. More preferably, the surface area of the support material is in the range of from about 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 μm. Most preferably, the surface area of the support material is in the range from about 100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 μm. The average pore size of the support material useful in the invention is in the range of from 10 to 1000 Å, preferably 50 to about 500 Å, and most preferably 75 to about 350 Å. In some embodiments, the support material is a high surface area, amorphous silica (surface area=300 m²/gm; pore volume of 1.65 cm³gm). Useful silicas are marketed under the trade names of DAVISON™ 952, DAVISON™ 948 or DAVISON™ 955 by the Davison Chemical Division of W.R. Grace and Company. Total surface area, also referred to as “surface area” and total pore volume, also referred to as “pore volume”, and average pore diameter are measured by the Brunauer-Emmett-Teller (BET) method using adsorption-desorption of nitrogen (temperature of liquid nitrogen, 77 K) with a Micromeritics Tristar II 3020 instrument after degassing of the powders for 4 hrs. at 350° C. More information regarding the method can be found, for example, in “Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density”, S. Lowell et al., Springer, 2004. Average particle size, also referred to as “particle size,” or “particle diameter” is determined using a Mastersizer™ 3000 (range of 1 to 3500 μm) available from Malvern Instruments, Ltd. Worcestershire, England.

In a particularly useful embodiment, the support is silica, is desirably porous, and has a surface area in the range of from about 10 to about 800 m²/g, a total pore volume in the range of from about 0.1 to about 4.0 cc/g and an average particle diameter in the range of from about 10 to about 500 μm. More desirably, the surface area is in the range of from about 50 to about 500 m²/g, the pore volume is in the range of from about 0.5 to about 3.5 cc/g and the average particle diameter is in the range of from about 15 to about 150 μm. Most desirably the surface area is in the range of from about 100 to about 400 m²/g, the pore volume is in the range of from about 0.8 to about 3.0 cc/g and the average particle diameter is in the range of from about 20 to about 100 μm. The average pore diameter of typical, porous silicon dioxide support materials is in the range of from about 10 to about 1000 Å. Desirably, the support material has an average pore diameter of from about 50 to about 500 Å, and most desirably from about 75 to about 350 Å.

The fluorine compounds suitable for providing fluorine for the support may be organic or inorganic fluorine compounds and are desirably inorganic fluorine containing compounds. Such inorganic fluorine containing compounds may be any compound containing a fluorine atom as long as it does not contain a carbon atom. Particularly desirable are inorganic fluorine-containing compounds selected from the group consisting of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆, GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₅, ClF₅, BrF₅, IF₇, NF₃, HF, BF₃, NHF₂ and NH₄HF₂. Of these, ammonium hexafluorosilicate and ammonium tetrafluoroborate are useful. Combinations of these compounds may also be used.

Ammonium hexafluorosilicate and ammonium tetrafluoroborate fluorine compounds are typically solid particulates as are the silicon dioxide supports. A useful method of treating the support with the fluorine compound is to dry mix the two components by simply blending at a concentration of from 0.01 to 10.0 millimole F/g of support, desirably in the range of from 0.05 to 6.0 millimole F/g of support, and most desirably in the range of from 0.1 to 3.0 millimole F/g of support. The fluorine compound can be dry mixed with the support either before or after charging to a vessel for dehydration or calcining the support. Accordingly, the fluorine concentration present on the support is preferably in the range of from 0.1 to 25 wt %, alternately 0.19 to 19 wt %, alternately from 0.6 to 3.5 wt %, based upon the weight of the support.

Another method of treating the support with the fluorine compound is to dissolve the fluorine compound in a solvent, such as water, and then contact the support (dry or combined with water or hydrocarbon solvent) with the fluorine compound containing solution. When water is used and silica is the support, it is desirable to use a quantity of water which is less than the total pore volume of the support.

A disadvantage of typical dry mix methods is that the density difference between fluorinating agent (such as ammonium hexafluorosilicate—density about 2.1 g/cm³) and silica (e.g., such as Davison™ 948—density about 0.7 g/cm³) makes it difficult to evenly/homogeneously distribute the fluorinating agent in the silica support. The density difference has also led to settling of ammonium hexafluorosilicate in fluorided silica derived from dry mix method. Over a period of two weeks, a vertical gradient of ammonium hexafluorosilicate concentrations in fluorided silica (made via dry mix method) stored in a bottle was observed. Such settling can lead to operational problems on a commercial scale.

To overcome these problems, an alternative method (wet-mixing) has been developed. The aqueous (wet-mixing) method employs a minimal amount of a polar solvent (e.g., water, or methanol, ethanol, isopropanol, any solvent capable of dissolving the fluoride compound (such as ammonium hexafluorosilicate) to dissolve the fluorinating agent (e.g., ammonium hexafluorosilicate). The fluoride compound solution (such as an ammonium hexafluorosilicate solution) is then added to a slurry of silica in a non-polar solvent (e.g., toluene, or benzene, chloroform, etc.), followed by vigorous stirring of the resulting mixture. The polar/hydrophilic nature of the fluoride compound (such as ammonium hexafluorosilicate) leads to its absorption onto the hydrophilic silica surface. When the non-polar solvent is removed (by filtration), silica with an even distribution of fluorinating agent (such as ammonium hexafluorosilicate) is obtained, and ready for subsequent drying and calcination steps.

This method reduces or eliminates non-homogeneous distribution of fluorinating agent in silica associated with other methods. In addition, fluorided silica prepared via wet-mixing method gave excellent operability, whereas fluorided silica prepared via dry-mixing method often gave poor operability due to frequent plugging of catalyst feed line.

Dehydration or calcining of the silica is not necessary prior to reaction with the fluorine compound, but can be done if desired. Desirably the reaction between the silica and fluorine compound is carried out at a temperature of from about 100° C. to about 400° C., and more desirably from about 150° C. to about 350° C. for about two to eight hours.

In one embodiment, the fluorided support composition may be generically represented by the formula: Sup-F, where “Sup” is a support, “F” is a fluorine atom bound to the support. The fluorine atom may be bound, directly or indirectly, chemically or physically to the support. An example of chemical or physical bonding would be covalent and ionic bonding, respectively.

In another embodiment, the fluorided support composition is represented by the formula: Sup-LF_(n), where “Sup” is a support, preferably selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria, aluminum phosphate gel, polyvinylchloride and substituted polystyrene; “L” is a first member selected from the group consisting of (i) bonding, sufficient to bound the F to the Sup; (ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, Al, or Zr bound to the Sup and to the F; and (iii) O bound to the Sup and bound to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, Al, or Zr which is bound to the F; “F” is a fluorine atom; and “n” is a number from 1-7.

An example of such bonding sufficient to bound the F to the Sup would be chemical or physical bonding, such as, for example, covalent and ionic bonding.

The fluorided support material is then typically slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a metallocene compounds and activator. In some embodiments, the slurry of the fluorided support material is first contacted with the activator for a period of time in the range of from about 0.5 hours to about 24 hours, from about 1 hour to about 16 hours, or from about 2 hours to about 8 hours. The solution of the metallocene compound is then contacted with the isolated fluorided support/activator. In some embodiments, the supported catalyst system is generated in situ. In alternate embodiment, the slurry of the fluorided support material is first contacted with the catalyst compound for a period of time in the range of from about 0.5 hours to about 24 hours, from about 1 hour (or 2 hours) to about 16 hours, or from about 2 hours (or 4 hours) to about 8 hours. The slurry of the supported metallocene compound is then contacted with the activator solution.

The mixture of the metallocenes, activator and flourided support may be heated to about 0° C. to about 70° C., preferably to about 23° C. to about 60° C., preferably at room temperature. Contact times typically range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

In a preferred embodiment of the invention, the flourided support material in slurried in a non-polar solvent and the resulting slurry is contacted with a solution of methylalumoxane (typically 30 wt % MAO in toluene). The flourided support/MAO mixture is then heated to elevated temperature (30° C. to 120° C., preferably 80 to 100° C.) with vigorous stirring for a period of time (0.1 to 24 hours, preferably 1 to 3 hours). The support/activator is isolated by filtration, rinsed with non-polar solvent (e.g., toluene, pentane, hexane, etc.), and dried. The isolated support/activator is then slurried in a non-polar solvent (e.g., toluene), and a solution of metallocene compound/compounds is then contacted with the support/activator slurry. Vigorous stirring may then be applied.

In a preferred embodiment of the invention, the flourided support material is slowly added in solid form to a solution of MAO in non-polar solvent (e.g., toluene) (typically at room temperature) with vigorous stirring. This addition sequence, namely slow and portion-wise addition of flourided silica to MAO solution, is referred to as “reversed addition”. After the addition of flourided silica is completed, the flourided support/MAO mixture is then heated to elevated temperature (30° C. to 120° C., preferably 80 to 100° C.) with vigorous stirring for a period of time (0.1 to 24 hours, preferably 1 to 3 hours). The support/activator is isolated by filtration, rinsed with non-polar solvent (e.g., toluene, pentane, hexane, etc.), and dried. The isolated support/activator is then slurried in a non-polar solvent (e.g., toluene), and a solution of metallocene compound/compounds is then contacted with the support/activator slurry. Vigorous stirring may be applied.

Under otherwise identical conditions, the “reversed addition” method for immobilizing MAO on flourided silica surface offers higher polymerization activity for a wide variety of catalysts, compared to the “traditional addition” method where MAO solution is added to a slurry of flourided silica in non-polar solvent.

Suitable non-polar solvents are materials in which all of the reactants used herein, i.e., the activator, and the metallocene compound, are at least partially soluble and which are liquid at reaction temperatures. Preferred non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed.

In a preferred embodiment of the invention, the flourided supports described herein are prepared by combining an aqueous solution of fluorinating agent (such as (NH₄)₂SiF₆) with a slurry of support (such as a toluene slurry of silica), drying until free flowing, optionally, calcining (typically at temperatures from 100° C. to 400° C. for at least 1 hour), then combining with activators and catalyst compounds (the activators and catalyst compounds may be added to the support separately or together).

In another embodiment of the invention, the water to solvent ratio (by weight) is between 1:10 to 1:1000, preferably between 1:20 to 1:50.

In another embodiment of the invention, the flourided silica support can immobilize greater than 5.0 mmol “Al” per gram silica, and preferably greater than 6.0 mmol “Al”/gram silica. The amount of “Al” (from alkylalumoxane, such as MAO) that can be immobilized on 1 gram of flourided silica is determined by an aluminum titration experiment. The titration is done at 100° C. at ambient pressure allowing the alumoxane (15 mmol Al) and the 1 gram of flourided silica to react for 3 hours. Thereafter, the silica is washed with toluene (10 ml, 3 times) and then washed with pentane (10 ml, 3 times). The solid is then collected and dried in vacuo for 8 hours until solvent is removed. Then the sample is weighed and the difference in weight is divided by the Mw of the aluminum compound (Mw as reported in the CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985)). Methyl alumoxane is defined to be Me-Al—O. The “Al” uptake for silica-1 in the examples below was about 5.5 mmol Al/gram, whereas the “Al” uptake for silica-2 was about 6.8 mmol/gram. Higher Al uptake (or loading) is often desirable as it is thought to offer higher polymerization activity, provided the silica and the catalyst precursor stay unchanged. In a useful embodiment of the invention, the catalyst system comprising the flourided silica support immobilizes greater than 5.0 mmol “Al” per gram of silica, and preferably greater than 6.0 mmol “Al” per gram of silica.

Alternately, the flourided silica support preferably contains less than 0.05 mmol/gram fluorinating agent (such as (NH₄)₂SiF₆), preferably less than 0.02 mmol/gram fluorinating agent, as measured by ¹H NMR.

Alternately, the surface area of the flourided silica support is greater than 200 m²/g, preferably greater than 250 m²/g, as determined by BET. Alternatively, the surface area of combined flourided silica support and activator (such as MAO) is greater than 250 m²/g, preferably greater than 350 m²/g, as determined by BET.

In embodiments where SiF₄ and/or (NH₄)₂SiF₆ is/are the fluoriding agent, immediately after combination of the alkylalumoxane with the fluorided support the combination preferably contains less than 0.04 mmoles pre gram of silica (preferably less than 0.02 mmoles, preferably less than 0.01 mmoles) of tetraalkylsilane per gram of support as determined by ¹H NMR (where the alkyl is derived from the alkylalumoxane).

In useful embodiments, the ratio of mmol of fluorine per gram of silica in the fluorided support is between 0.1 and 1.5, preferably between 0.2 and 1.2, preferably between 0.4 and 1.0.

For fluorided silica prepared using (NH₄)₂SiF₆, the amount of residual (NH₄)₂SiF₆ in the silica should be equal or less than 0.04 mmol (NH₄)₂SiF₆/g silica, preferably equal or less than 0.02 mmol (NH₄)₂SiF₆/g silica, more preferably equal or less than 0.01 mmol (NH₄)₂SiF₆/g silica.

Catalyst Compounds

Useful catalysts include compounds represented by the formula: T_(y)Cp_(m)MG_(n)X_(q) wherein Cp is a cyclopentadienyl group (such as cyclopentadiene, indene or fluorene) which may be substituted or unsubstituted, M is a Group 4 transition metal, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, G is a heteroatom group represented by the formula JR*_(Z) where J is a group 15 or 16 element, preferably N, P, O or S, and R* is a C₁ to C₂₀ hydrocarbyl group and z is 1 or 2, T is a bridging group, and y is 0 or 1, each X is, independently, a leaving group, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal (preferably 2, 3, 4, 5, or 6, preferably 4 or 5, preferably 4). In the present invention at least two metallocenes are present on the support where in the first metallocene m is 1, n is 1, and y is 1 and in the second metallocene n is 0 and m is 2, provided that when y=1 in the second metallocene compound, then at least one Cp is preferably not an indene group.

In a preferred embodiment of the invention, M is a Group 4 transition metal (preferably Hf, Ti and/or Zr) and the two catalyst compounds may have the same or different M. In an embodiment when M is Ti, then m is 1. In another embodiment when M is Zr, then m is 2 or 3. In an embodiment when M is Ti, then m is 1 and when M is Zr, then m is 2. In a useful embodiment, in the first metallocene M is Ti and in the second metallocene M is Hf or Zr.

Typically, each G is, independently, a heteroatom group represented by the formula JR*_(z) where J is a group 15 or 16 element, preferably N, P, O or S (preferably N or O, preferably N), and R* is a C₁ to C₂₀ hydrocarbyl group. Typically, a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof, including t-butyl, cyclododecyl, cyclooctyl and the like) and z is 1 or 2.

In an embodiment, when m is one, n is preferably 1 and G is a heteroatom group represented by the formula JR*_(z) where J is a group 15 or 16 element, preferably N, P, O or S (preferably N or O, preferably N), and R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, including t-butyl, cyclodecyl, cyclooctyl and the like) and z is 1 or 2, preferably JR*_(z) is cyclododecyl amido, t-butyl amido, and or 1-adamantylamido.

In an embodiment, when m is 2 or 3, n is 0.

In an embodiment each X may be, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.

Alternately, each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system), preferably each X is independently selected from halides, aryls and C₁ to C₅ alkyl groups, preferably each X is a phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloro group.

Typically, each Cp group is, independently, a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene, or a substituted or unsubstituted fluorene.

Independently, each Cp group may be substituted with a combination of substituent groups R. Non-limiting examples of substituent groups R include one or more from the group selected from hydrogen, or linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals, alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof. In a preferred embodiment, substituent groups R have up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, that can also be substituted with halogens or heteroatoms or the like. Non-limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example, tertiary butyl, isopropyl and the like. Other hydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)-silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted pnictogen radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide. Non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium and the like, including olefins such as, but not limited to, olefinically unsaturated substituents including vinyl-terminated ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups, preferably two adjacent R groups, may be joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron or a combination thereof.

In an embodiment of the Cp group, the substituent(s) R are, independently, hydrocarbyl groups, heteroatoms, or heteroatom containing groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, N, O, S, P, or a C₁ to C₂₀ hydrocarbyl substituted with an N, O, S and or P heteroatom or heteroatom containing group (typically having up to 12 atoms, including the N, O, S and P heteroatoms).

Non-limiting examples of Cp groups include cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraenyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine ligands (WO 99/40125), pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands. In another embodiment, each Cp may, independently comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorus, in combination with carbon atoms to form an open, acyclic, or preferably a fused, ring or ring system, for example, a heterocyclopentadienyl ancillary ligand. Other Cp ligands include but are not limited to porphyrins, phthalocyanines, corrins and other polyazamacrocycles.

Preferably, T is present and is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular boron or a Group 14, 15 or 16 element. Examples of suitable bridging groups include P(═S)R′, P(═Se)R′, P(═O)R′, R′₂C, R′₂Si, R′₂Ge, R′₂CCR′₂, R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′, R′C═CR′CR′₂, R′₂CCR′═CR′CR′₂, R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂, R′₂CSiR′₂, R′₂SiSiR′₂, R′₂SiOSiR′₂, R′₂CSiR′₂CR′₂, R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂, R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂, R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂, R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂, R′₂C—O—CR′₂, R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂, R′₂C—O—CR′═CR′, R′₂C—S—CR′₂, R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′, R′₂C—Se—CR′₂, R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′═CR′, R′₂C—N═CR′, R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′, R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, R′₂C—PR′—CR′₂, O, S, Se, Te, NR PR′, AsR′, SbR′, O—O, S—S, R′N—NR′, R′P—PR′, O—S, O—NR′, O—PR′, S—NR′, S—PR′, and R′N—PR′ where R′ is hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R′ may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or poly cyclic substituent. Preferred examples for the bridging group T include CH₂, CH₂CH₂, SiMe₂, SiPh₂, SiMePh, Si(CH₂)₃, Si(CH₂)₄, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu.

In a preferred embodiment of the invention in any embodiment of any formula described herein, T is represented by the formula R₂ ^(a)J or (R₂ ^(a)J)₂, where J is C, Si, or Ge, and each R^(a) is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C₁ to C₂₀ substituted hydrocarbyl, and two R^(a) can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system. Preferably, T is a bridging group comprising carbon or silica, such as dialkylsilyl, preferably T is selected from CH₂, CH₂CH₂, C(CH₃)₂, SiMe₂, SiPh₂, SiMePh, silylcyclobutyl (Si(CH₂)₃), (Ph)₂C, (p-(Et)₃SiPh)₂C, Me₂SiOSiMe₂, and cyclopentasilylene (Si(CH₂)₄).

Useful bridged metallocene compounds having one cyclopentadienyl ring include those represented by the formula:

wherein

-   M is the same as M described above, preferably M is titanium,     zirconium or hafnium, preferably titanium; -   Z is a substituted or unsubstituted Cp group (useful Z groups are     represented by the formula: (C₅H_(4-d)S*_(d)), where d is 1, 2, 3 or     4, S* is hydrocarbyl groups, heteroatoms, or heteroatom containing     groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,     octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, N, O, S,     P, or a C₁ to C₂₀ hydrocarbyl substituted with an N, O, S and or P     heteroatom or heteroatom containing group (typically having up to 12     atoms, including the N, O, S and P heteroatoms) and two S* may form     a cyclic or multicyclic group, preferably Z is     tetramethylcyclopentadienyl; -   T is a bridging group as described above that is bonded to Z and Q,     y is one; -   Q is a heteroatom with a coordination number of three from Group 15     or with a coordination number of two from Group 16 of the Periodic     Table of Elements, such as N, O, S or P and preferably Q is     nitrogen; -   R″ is selected from a C₃-C₁₀₀ substituted or unsubstituted     monocyclic or polycyclic ring structure substituent that is     partially unsaturated, unsaturated or aromatic; or a C₂-C₁₀₀     substituted or unsubstituted, unsaturated or partially unsaturated,     linear or branched alicyclic hydrocarbyl substituent; or a C₁-C₁₀₀     substituted or unsubstituted saturated hydrocarbyl radical     (preferably R″ is selected from methyl, ethyl, all propyl isomers,     all butyl isomers, phenyl, benzyl, phenethyl, 1-adamantyl,     cyclododecyl, cyclohexyl and norbornyl); -   t is the coordination number of the heteroatom Q where “t-1-y”     indicates the number of R″ substituents bonded to Q; and -   each X is, independently, a univalent anionic ligand, or two X are     joined and bound to the metal atom to form a metallocycle ring, or     two X are joined to form a chelating ligand, a diene ligand, or an     alkylidene ligand.

Illustrative, but not limiting, examples of preferred monocyclopentadienyl metallocenes for use in this invention's mixed catalyst composition include:

-   dimethylsilyl     (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl, -   dimethylsilyl     (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride, -   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium     dimethyl, -   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium     dichloride, -   μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)₂; -   μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)₂; -   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂; -   μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂; -   μ-(CH₃)₂Si(η⁵-2.6.6-trimethyl-1.5.6.7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M(R)₂; -   where M is selected from a group consisting of Ti, Zr, and Hf and R     is selected from halogen -   or C1 to C5 alkyl, preferably R is a methyl group.

Useful metallocenes having two or three cyclopentadienyl rings are represented by the formula:

wherein

-   M is the same as M described above, preferably M is titanium,     zirconium or hafnium, Zr or Hf; -   Z and Q* are, independently, a substituted or unsubstituted Cp group     (useful Z and Q* groups are represented by the formula:     (C₅H_(4-d)S*_(d)), where d is 1, 2, 3 or 4, S* is hydrocarbyl     groups, heteroatoms, or heteroatom containing groups, such as     methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,     decyl, undecyl, dodecyl or an isomer thereof, N, O, S, P, or a C₁ to     C₂₀ hydrocarbyl substituted with an N, O, S and or P heteroatom or     heteroatom containing group (typically having up to 12 atoms,     including the N, O, S and P heteroatoms) and two S* may form a     cyclic or multicyclic group; -   T is a bridging group as described above that is bonded to Z and Q*,     y is zero or one; and -   each X is, independently, a univalent anionic ligand, or two X are     joined and bound to the metal atom to form a metallocycle ring, or     two X are joined to form a chelating ligand, a diene ligand, or an     alkylidene ligand provided that when y is one then at least one of Z     and Q* is preferably not an indene group, alternately both of Z and     Q* are not indene. In an alternate embodiment, when y is one, Z and     Q* are not 2, 4 substituted indene, preferably are not 2-methyl,     4-phenyl indene.

Particularly useful biscyclopentadienyl catalysts include:

-   Bis(tetrahydroindene)Hf Me₂; -   Bis(1-butyl,3-methylcyclopentadienyl)ZrCl₂; -   Bis-(n-butylcyclopentadienyl)ZrCl₂; -   (Dimethylsilyl)₂O bis(indenyl)ZrCl₂; -   Dimethylsilyl(3-(3-methylbutyl)cyclopentadienyl)(2,3,4,5-tetramethylcyclopentadienyl)ZrCl₂; -   Dimethylsilylbis(tetrahydroindenyl)ZrCl₂; -   Dimethylsilyl-(3-phenyl-indenyl)(tetramethylcyclopentadienyl)ZrCl₂; -   Dimethylsilyl(3-neopentylcyclopentadienyl)(tetramethylcyclopentadienyl)HfCl₂; -   Tetramethyldisilylene bis(4-(3,5-di-tert-butylphenyl)-indenyl)ZrCl₂;     and -   Cyclopentadienyl(1,3-diphenylcyclopentadienyl)ZrCl₂.

Particularly useful metallocenes are those selected from the group consisting of: bis(cyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)hafnium dichloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl, bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl, bis(tetrahydro-1-indenyl)zirconium dichloride, bis(tetrahydro-1-indenyl)zirconium dimethyl, dimethylsilylbis(tetrahydroindenyl)zirconium dichloride, dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl, dimethylsilylbis(indenyl)zirconium dichloride, dimethylsilyl(bisindenyl)zirconium dimethyl, dimethylsilylbis(cyclopentadienyl)zirconium dichloride, and dimethylsilylbis(cyclopentadienyl)zirconium dimethyl.

Particularly useful combinations of catalysts include:

-   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and bis(1-Bu,3-Me-Cp) ZrCl₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂) bis(indenyl)ZrCl₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrCl₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrMe₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and SiMe₂(3-neopentylCp)((Me₄Cp)HfCl₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and     SiMe₂(3-neopentylcyclopentadienyl)(Me₄Cp)HfMe₂; -   SiMe₂(Me₄Cp)(1-adamantylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂; and -   SiMe₂(Me₄Cp)(1-t-butylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂.

In a useful embodiment a third catalyst is present, such as (Me₂Si)₂O(Ind)₂ZrCl₂, 2,6-Bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride, typically the third catalyst is a different metallocene.

For purposes of this invention one metallocene catalyst compound is considered different from another if they differ by at least one atom. For example “bisindenyl zirconium dichloride” is different from (indenyl)(2-methylindenyl) zirconium dichloride” which is different from “(indenyl)(2-methylindenyl) hafnium dichloride.” Catalyst compounds that differ only by isomer are considered the same for purposes of this invention, e.g., rac-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl is considered to be the same as meso-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl.

Synthesis of monocyclopentadienyl complexes is known in the art, and for example, has been disclosed in WO 93/19103, U.S. Pat. No. 5,096,867 and U.S. Pat. No. 5,264,405.

Synthesis of bis cyclopentadienyl complexes is known in the art, and for example, has been disclosed in U.S. Pat. No. 4,530,914; U.S. Pat. No. 4,542,199; U.S. Pat. No. 4,769,910; U.S. Pat. No. 4,808,561; U.S. Pat. No. 4,871,705; U.S. Pat. No. 4,933,403; U.S. Pat. No. 4,937,299; U.S. Pat. No. 5,017,714; U.S. Pat. No. 5,026,798; U.S. Pat. No. 5,057,475; U.S. Pat. No. 5,120,867; U.S. Pat. No. 5,278,119; U.S. Pat. No. 5,304,614; U.S. Pat. No. 5,324,800; U.S. Pat. No. 5,350,723; U.S. Pat. No. 5,391,790; and U.S. Pat. No. 7,141,632, each fully incorporated herein by reference.

Activators

The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation. Non-limiting activators, for example, include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. Preferred activators typically include alumoxane compounds, modified alumoxane compounds, used alone or in combination with ionizing anion precursor compounds that abstract a reactive, σ-bound, metal ligand making the metal complex cationic and providing a charge-balancing noncoordinating or weakly coordinating anion.

Alumoxane Activators

Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally oligomeric compounds containing —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator typically at up to a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site). The minimum activator-to-catalyst-compound is a 1:1 molar ratio. Alternate preferred ranges include from 1:1 to 500:1, alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, or alternately from 1:1 to 50:1.

Non Coordinating Anion Activators

In alternate embodiments, the alkylalumoxanes can be sued in combination with non-coordinating anion activators. The term “non-coordinating anion” (NCA) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization.

It is within the scope of this invention to use an ionizing or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenyl boron metalloid precursor or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat. No. 5,942,459), in combination with the alumoxane or modified alumoxane activators. It is also within the scope of this invention to use neutral or ionic activators in combination with the alumoxane or modified alumoxane activators.

The catalyst systems of this invention can include at least one non-coordinating anion (NCA) activator. Specifically, the catalyst systems may include an NCA which either do not coordinate to a cation or which only weakly coordinate to a cation thereby remaining sufficiently labile to be displaced during polymerization.

The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.

In a preferred embodiment boron containing NCA activators represented by the formula below can be used:

Z_(d) ⁺(A^(d−))

where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A^(d−) is a boron containing non-coordinating anion having the charge d−; d is 1, 2, or 3.

The cation component, Z_(d) ⁺ may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species.

The activating cation Z_(d) ⁺ may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably Z_(d) ⁺ is triphenyl carbonium. Preferred reducible Lewis acids can be any triaryl carbonium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C1 to C40 hydrocarbyl), preferably the reducible Lewis acids in formula (14) above as “Z” include those represented by the formula: (Ph₃C), where Ph is a substituted or unsubstituted phenyl, preferably substituted with C₁ to C₄₀ hydrocarbyls or substituted a C₁ to C₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics, preferably Z is a triphenylcarbonium.

When Z_(d) ⁺ is the activating cation (L-H)_(d) ⁺, it is preferably a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof.

The anion component Ad includes those having the formula [M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); n−k=d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group. Examples of suitable A^(d−) also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.

Illustrative, but not limiting examples of boron compounds which may be used as an activating cocatalyst are the compounds described as (and particularly those specifically listed as) activators in U.S. Pat. No. 8,658,556, which is incorporated by reference herein.

Most preferably, the ionic stoichiometric activator Z_(d) ⁺(A^(d−)) is one or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluorophenyl)borate.

Bulky activators are also useful herein as NCAs. “Bulky activator” as used herein refers to anionic activators represented by the formula:

where:

-   each R₁ is, independently, a halide, preferably a fluoride; -   Ar is substituted or unsubstituted aryl group (preferably a     substituted or unsubstituted phenyl), preferably substituted with C₁     to C₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls or aromatics; each     R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatic     hydrocarbyl group or a siloxy group of the formula —O—Si—R_(a),     where R^(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group     (preferably R₂ is a fluoride or a perfluorinated phenyl group); -   each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl     group or a siloxy group of the formula —O—Si—R_(a), where R^(a) is a     C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a     fluoride or a C₆ perfluorinated aromatic hydrocarbyl group); wherein     R₂ and R₃ can form one or more saturated or unsaturated, substituted     or unsubstituted rings (preferably R₂ and R₃ form a perfluorinated     phenyl ring); and -   L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or     3; -   wherein the anion has a molecular weight of greater than 1020 g/mol;     wherein at least three of the substituents on the B atom each have a     molecular volume of greater than 250 cubic Å, alternately greater     than 300 cubic Å, or alternately greater than 500 cubic Å.

Preferably (Ar₃C)_(d) ⁺ is (Ph₃C)_(d) ⁺, where Ph is a substituted or unsubstituted phenyl, preferably substituted with C₁ to C₄₀ hydrocarbyls or substituted C₁ to C₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics.

“Molecular volume” is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of the Envelope” Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å, is calculated using the formula: MV=8.3V_(S), where V_(S) is the scaled volume. V_(S) is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the V_(S) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) short period, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rb to I 7.5 3^(rd) long period, Cs to Bi 9

For a list of particularly useful Bulky activators, please see U.S. Pat. No. 8,658,556, which is incorporated by reference herein.

In another embodiment, one or more of the NCA activators is chosen from the activators described in U.S. Pat. No. 6,211,105.

Preferred activators include N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄ ⁻]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6- tetrafluorophenyl)pyrrolidinium; and tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl).

The typical NCA activator-to-catalyst ratio, e.g., all NCA activators-to-catalyst ratio is about a 1:1 molar ratio. Alternate preferred ranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1. A particularly useful range is from 0.5:1 to 10:1, preferably 1:1 to 5:1.

It is also within the scope of this invention that the catalyst compounds can be combined with combinations of alumoxanes and NCA's (see for example, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,453,410, EP 0 573 120 B1, WO 94/07928, and WO 95/14044 which discuss the use of an alumoxane in combination with an ionizing activator).

Optional Scavengers or Co-Activators

In addition to the activator compounds, scavengers, chain transfer agents or co-activators may be used. Aluminum alkyl or organoaluminum compounds which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

Useful chain transfer agents that may also be used herein are typically a compound represented by the formula AlR₃, ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

Preparation of the Supported Catalyst

In an embodiment, this invention describes the preparation of fluorided supports (such as silica) through the addition of a solution of polar solvent (such as water) and fluorine compound (such as (NH₄)₂SiF₆) to a slurry of support (such as a toluene slurry of silica). This preparation method contributes to an even distribution of the fluoride compound (such as (NH₄)₂SiF₆) onto the support surface (such as the silica surface), in contrast to a less homogeneous distribution observed when the solid salt is combined with the solid silica as described in U.S. Publication No. 2002/0123582 A1. Metallocenes supported on the flourided support from this preparation exhibit comparable or higher activity compared to supported metallocenes on flourided supports made through solid/solid mixing.

In an embodiment, a solution of polar solvent (such as water) and fluorinating agent (such as (NH₄)₂SiF₆) is added to a slurry of support (such as a toluene slurry of silica). Vigorous stirring of the mixture allows the dissolved fluorine compound (preferably in water) to be evenly absorbed onto the hydrophilic support surface. After filtration, the wet support is allowed to air dry until it is free flowing, and then may be calcined (typically at temperatures over 100° C. for at least 1 hour).

In a particularly useful embodiment of the invention, the catalyst systems described herein are prepared by:

-   1. Fluorided silica preparation: The wet mix method typically     employs a minimal amount of a polar solvent (e.g., water, or     methanol, ethanol, isopropanol, any solvent capable of dissolving     the fluoride compound (such as ammonium hexafluorosilicate) to     dissolve the fluorinating agent (such as ammonium     hexafluorosilicate), but can use an excess of solvent if desired.     The solution (typically ammonium hexafluorosilicate solution) is     then added to a slurry of silica in a non-polar solvent (e.g.,     toluene, or benzene, chloroform, etc.), followed by vigorous     stirring of the resulting mixture. The polar/hydrophilic nature of     the fluorinating agent (such as ammonium hexafluorosilicate) leads     to its absorption onto the hydrophilic silica surface. When the     non-polar sol vent is removed (by filtration), silica with an even     distribution of fluorinating agent (such as ammonium     hexafluorosilicate) is obtained, and ready for subsequent drying and     calcination steps. -   2a. Immobilization of alumoxane on flourided silica: In a preferred     embodiment of the invention, the flourided support material in then     slurried in a non-polar solvent and the resulting slurry is     contacted with a solution of alumoxane (such as methylalumoxane).     The flourided support/alumoxane mixture is then heated to elevated     temperature (30° C. to 120° C., preferably 80-100° C.) with vigorous     stirring for a period of time (0.1 to 24 hours, preferably 1 to 3     hours). The support/activator is isolated by filtration, rinsed with     non-polar solvent (e.g., toluene, pentane, hexane, etc.), and dried.     The isolated support/activator is then slurried in a non-polar     solvent (e.g., toluene), and a solution of metallocene     compound/compounds is then contacted with the support/activator     slurry. Vigorous stirring is typically applied. -   2b. Immobilization of flourided silica in solid form: In an     alternate embodiment of the invention, the flourided support     material may be slowly added in solid form to a solution of     alumoxane in non-polar solvent (e.g., toluene) (typically at room     temperature) with vigorous stirring. This addition sequence, namely     slow and portion-wise addition of fluorided silica to the alumoxane     solution, is referred to as “reversed addition”. After the addition     of fluorided silica is completed, the fluorided support/alumoxane     mixture is then heated to elevated temperature (30° C. to 120° C.,     preferably 80° C. to 100° C.) with vigorous stirring for a period of     time (0.1 to 24 hours, preferably 1 to 3 hours). The     support/activator is then isolated by filtration, rinsed with     non-polar solvent (e.g., toluene, pentane, hexane, etc.), and dried.     The isolated support/activator is then slurried in a non-polar     solvent (e.g., toluene), and a solution of metallocene     compound/compounds is then contacted with the support/activator     slurry. Vigorous stirring is typically applied. Under otherwise     identical condition, the reversed addition method for immobilizing     MAO on fluorided silica surface offers higher polymerization     activity for a wide variety of catalysts, compared to the     “traditional addition” method where methylalumoxane solution is     added to a slurry of fluorided silica in non-polar solvent. -   3. Activation and supportation of metallocenes on silica/MAO     support: The silica/MAO support/activator generated in the MAO     immobilization step 2 (a or b) is slurried in a non-polar solvent     (e.g., toluene). The resulting slurry is then contacted with a     solution of metallocenes (two metallocene precursors or more) with     vigorous stirring. The mixture is stirred for 0.5 hour to 24 hours     (preferably for 1 to 3 hours) at temperature between 23° C. to     110° C. (preferably at 20° C. to 40° C.). The finished supported     catalyst is then isolated by filtration, rinsed with non-polar     solvent (e.g., toluene, pentane), and dried. -   4. The metallocene precursors can be dissolved together with solvent     to create one solution, or each metallocene can be dissolved     individually. -   5. The multiple metallocene precursors can be added to     silica/alumoxane support/activator slurry together in one solution,     or individual solution of each metallocene precursor can be added in     any order/sequence. In a preferred embodiment of the invention, the     multiple metallocene precursors are added to silica/alumoxane     support/activator slurry together in one solution.

Polymerization Processes

In embodiments herein, the invention relates to polymerization processes where monomer (such as ethylene), and optionally comonomer (such as hexene), are contacted with a catalyst system comprising the result of the combination of an activator, a fluorided support, and at least two metallocene compounds, as described above. The catalyst compounds, support and activator may be combined in any order, and are combined typically prior to contacting with the monomer.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀ alpha olefins, preferably C₂ to C₂₀ alpha olefins, preferably C₂ to C₁₂ alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In a preferred embodiment of the invention, the monomers comprises ethylene and optional comonomers comprising one or more C₃ to C₄₀ olefins, preferably C₄ to C₂₀ olefins, or preferably C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

Exemplary C₃ to C₄₀ comonomers include propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbomene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives.

In a preferred embodiment one or more dienes are present in the polymer produced herein at up to 10 weight %, preferably at 0.00001 to 1.0 weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003 to 0.2 weight %, based upon the total weight of the composition. In some embodiments 500 ppm or less of diene is added to the polymerization, preferably 400 ppm or less, preferably or 300 ppm or less. In other embodiments at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.

Preferred diolefin monomers useful in this invention include any hydrocarbon structure, preferably C4 to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further preferred that the diolefin monomers be selected from alpha, omega-diene monomers (i.e. di-vinyl monomers). More preferably, the diolefin monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms. Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g/mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbomadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.

In a particularly preferred embodiment the process of the invention relates to the polymerization of ethylene and at least one comonomer having from 3 to 8 carbon atoms, preferably 4 to 8 carbon atoms. Particularly, the comonomers are propylene, butene-1, 4-methyl-pentene-1,3-methyl-pentene-1, hexene-1 and octene-1, the most preferred being hexene-1, butene-1 and octene-1.

Polymerization processes of this invention can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Gas phase polymerization processes and slurry processes are preferred. (A homogeneous polymerization process is defined to be a process where at least 90 wt % of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is defined to be a process where monomer concentration in all feeds to the reactor is 70 volume % or more.) Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene). In another embodiment, the process is a slurry process. As used herein the term “slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt % of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™); perhalogenated hydrocarbons, such as perfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic and alkyl substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, preferably aromatics are present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, preferably less than 0 wt % based upon the weight of the solvents.

In a preferred embodiment, the feed concentration of the monomers and comonomers for the polymerization is 60 vol % solvent or less, preferably 40 vol % or less, or preferably 20 vol % or less, based on the total volume of the feedstream. Preferably the polymerization is run in a bulk process.

Preferred polymerizations can be run at any temperature and/or pressure suitable to obtain the desired polymers. Typical temperatures and/or pressures include a temperature in the range of from about 0° C. to about 300° C., preferably about 20° C. to about 200° C., preferably about 35° C. to about 150° C., preferably from about 40° C. to about 120° C., preferably from about 45° C. to about 80° C; and at a pressure in the range of from about 0.35 MPa to about 10 MPa, preferably from about 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about 4 MPa.

In a typical polymerization, the run time of the reaction is up to 300 minutes, preferably in the range of from about 5 to 250 minutes, or preferably from about 10 to 120 minutes.

In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa).

In an alternate embodiment, the activity of the catalyst is at least 800 gpolymer/gsupported catalyst/hour, preferably 1000 or more gpolymer/gsupported catalyst/hour, preferably 100 or more gpolymer/gsupported catalyst/hour, preferably 1600 or more gpolymer/gsupported catalyst/hour.

In a preferred embodiment, little or no scavenger is used in the process to produce the ethylene polymer. Preferably, scavenger (such as tri alkyl aluminum) is present at zero mol %, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1.

In a preferred embodiment, the polymerization: 1) is conducted at temperatures of 0 to 300° C. (preferably 25° C. to 150° C., preferably 40° C. to 120° C., preferably 45° C. to 80° C.); 2) is conducted at a pressure of atmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably where aromatics are preferably present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, preferably at 0 wt % based upon the weight of the solvents); 4) the polymerization preferably occurs in one reaction zone; and 5) optionally hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa) (preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)).

A “reaction zone” also referred to as a “polymerization zone” is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In a preferred embodiment, the polymerization occurs in one reaction zone. Room temperature is 23° C. unless otherwise noted.

Gas Phase Polymerization

Generally, in a fluidized gas bed process used for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (See for example U.S. Pat. No. 4,543,399; U.S. Pat. No. 4,588,790; U.S. Pat. No. 5,028,670; U.S. Pat. No. 5,317,036; U.S. Pat. No. 5,352,749; U.S. Pat. No. 5,405,922; U.S. Pat. No. 5,436,304; U.S. Pat. No. 5,453,471; U.S. Pat. No. 5,462,999; U.S. Pat. No. 5,616,661; and U.S. Pat. No. 5,668,228; all of which are fully incorporated herein by reference.)

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50 atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) or even greater and temperatures in the range of 0° C. to about 120° C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomers, along with catalysts, are added. The suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used, the process must be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an isobutane medium is employed.

In an embodiment, a preferred polymerization technique useful in the invention is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution. Such technique is well known in the art, and described in for instance U.S. Pat. No. 3,248,179, which is fully incorporated herein by reference. The preferred temperature in the particle form process is within the range of about 85° C. to about 110° C. Two preferred polymerization methods for the slurry process are those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Also, other examples of slurry processes are described in U.S. Pat. No. 4,613,484, which is herein fully incorporated by reference.

In another embodiment, the slurry process is carried out continuously in a loop reactor. The catalyst, as a slurry in isobutane or as a dry free flowing powder, is injected regularly to the reactor loop, which is itself filled with circulating slurry of growing polymer particles in a diluent of isobutane containing monomer and comonomer. Hydrogen, optionally, may be added as a molecular weight control. (In one embodiment 500 ppm or less of hydrogen is added, or 400 ppm or less or 300 ppm or less. In other embodiments at least 50 ppm of hydrogen is added, or 100 ppm or more, or 150 ppm or more.)

The reactor may be maintained at a pressure of 3620 kPa to 4309 kPa and at a temperature in the range of about 60° C. to about 104° C. depending on the desired polymer melting characteristics. Reaction heat is removed through the loop wall since much of the reactor is in the form of a double-jacketed pipe. The slurry is allowed to exit the reactor at regular intervals or continuously to a heated low pressure flash vessel, rotary dryer and a nitrogen purge column in sequence for removal of the isobutane diluent and all unreacted monomer and comonomers. The resulting hydrocarbon free powder is then compounded for use in various applications.

Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.

Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AlR₃, ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

Polyolefin Products

This invention also relates to compositions of matter produced by the methods described herein.

In a preferred embodiment, the process described herein produces ethylene homopolymers or ethylene copolymers, such as ethylene-alphaolefin (preferably C₃ to C₂₀) copolymers (such as ethylene-butene copolymers, ethylene-hexene and/or ethylene-octene copolymers) having: a Mw/Mn of greater than 1 to 4 (preferably greater than 1 to 3).

Likewise, the process of this invention produces ethylene copolymers. In a preferred embodiment, the copolymers produced herein have from 0 to 25 mole % (alternately from 0.5 to 20 mole %, alternately from 1 to 15 mole %, preferably from 3 to 10 mole %) of one or more C₃ to C₂₀ olefin comonomer (preferably C₃ to C₁₂ alpha-olefin, preferably propylene, butene, hexene, octene, decene, dodecene, preferably propylene, butene, hexene, octene).

In a preferred embodiment, the monomer is ethylene and the comonomer is hexene, preferably from 1 to 15 mole % hexene, alternately 1 to 10 mole %.

Typically, the polymers produced herein have an Mw of 5,000 to 1,000,000 g/mol (preferably 25,000 to 750,000 g/mol, preferably 50,000 to 500,000 g/mol), and/or an Mw/Mn of greater than 1 to 40 (alternately 1.2 to 20, alternately 1.3 to 10, alternately 1.4 to 5, 1.5 to 4, alternately 1.5 to 3).

In a preferred embodiment, the polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromotography (GPC). By “unimodal” is meant that the GPC trace has one peak or inflection point. By “multimodal” is meant that the GPC trace has at least two peaks or inflection points. An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).

Unless otherwise indicated Mw, Mn, MWD are determined by GPC as described the Experimental section below.

In a preferred embodiment, the polymer produced herein has a composition distribution breadth index (CDBI) of 50% or more, preferably 60% or more, preferably 70 % or more. CDBI is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in WO 93/03093, published Feb. 18, 1993, specifically columns 7 and 8 as well as in Wild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Pat. No. 5,008,204, including that fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining CDBI.

In another embodiment, the polymer produced herein has two peaks in the TREF measurement (see below). Two peaks in the TREF measurement as used in this specification and the appended claims means the presence of two distinct normalized ELS (evaporation mass light scattering) response peaks in a graph of normalized ELS response (vertical or y axis) versus elution temperature (horizontal or x axis with temperature increasing from left to right) using the TREF method below. A “peak” in this context means where the general slope of the graph changes from positive to negative with increasing temperature. Between the two peaks is a local minimum in which the general slope of the graph changes from negative to positive with increasing temperature. “General trend” of the graph is intended to exclude the multiple local minimums and maximums that can occur in intervals of 2° C. or less. Preferably, the two distinct peaks are at least 3° C. apart, more preferably at least 4° C. apart, even more preferably at least 5° C. apart. Additionally, both of the distinct peaks occur at a temperature on the graph above 20° C. and below 120° C. where the elution temperature is run to 0° C. or lower. This limitation avoids confusion with the apparent peak on the graph at low temperature caused by material that remains soluble at the lowest elution temperature. Two peaks on such a graph indicates a bi-modal composition distribution (CD). Bimodal CD may also be determined by other methods known to those skilled in the art. One such alternate method for TREF measurement then can be used if the above method does not show two peaks is disclosed in B. Monrabal, “Crystallization Analysis Fractionation: A New Technique for the Analysis of Branching Distribution in Poly olefins,” Journal of Applied Polymer Science, Vol. 52, 491-499 (1994).

TREF Method

Temperature Rising Elution Fractionation (TREF) analysis is done using a CRYSTAF-TREF 200+ instrument from Polymer Char, S A., Valencia, Spain. The principles of TREF analysis and a general description of the particular apparatus to be used are given in the article Monrabal, B.; del Hierro, P. Anal. Bioanal. Chem. 2011, 399, 1557. FIG. 3 of the article is an appropriate schematic of the particular apparatus used; however, the connections to the 6-port valve shown in FIG. 3 differ from the apparatus to be used in that the tubing connected to the 11-o'clock port is connected to the 9-o'clock port and the tubing connected to the 9-o'clock port is connected to the 11-o'clock port. Pertinent details of the analysis method and features of the apparatus to be used are as follows.

1,2-Dichlorobenzene (ODCB) solvent stabilized with approximately 380 ppm of 2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxy toluene) is used for preparing the sample solution and for elution. The sample to be analyzed (approximately 25 mg but as low as approximately 10 mg) is dissolved in ODCB (25 ml metered at ambient temperature) by stirring at 150° C. for 60 min. A small volume (0.5 ml) of the solution is introduced into a column (15-cm long by ⅜″ o.d.) packed with an inert support (of stainless steel balls) at 150° C., and the column temperature is stabilized at 140° C. for 45 min. The sample volume is then allowed to crystallize in the column by reducing the temperature to 30° C. at a cooling rate of 1° C./min. The column is kept at 30° C. for 15 min before injecting the ODCB flow (1 ml/min) into the column for 10 min to elute and measure the polymer that did not crystallize (soluble fraction). The infrared detector used (Polymer Char IR4) generates an absorbance signal that is proportional to the concentration of polymer in the eluting flow. A complete TREF curve is then generated by increasing the temperature of the column from 30 to 140° C at a rate of 2° C./min while maintaining the ODCB flow at 1 ml/min to elute and measure the dissolving polymer.

Blends

In another embodiment, the polymer (preferably the ethylene-hexene copolymer) produced herein is combined with one or more additional polymers prior to being formed into a film, molded part or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, poly butene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic poly butene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

In a preferred embodiment, the polymer (preferably the polyethylene produced herein) is present in the above blends, at from 10 to 99 wt %, based upon the weight of the polymers in the blend, preferably 20 to 95 wt %, even more preferably at least 30 to 90 wt %, even more preferably at least 40 to 90 wt %, even more preferably at least 50 to 90 wt %, even more preferably at least 60 to 90 wt %, even more preferably at least 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of the invention with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer. The polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like.

Films

Specifically, any of the foregoing polymers, such as the foregoing ethylene copolymers or blends thereof, may be used in a variety of end-use applications. Such applications include, for example, mono- or multi-layer blown, extruded, and/or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the layers of the film may be oriented in the transverse and/or longitudinal directions to the same or different extents. The uniaxially orientation can be accomplished using typical cold drawing or hot drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further. Typically the films are oriented in the Machine Direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, preferably 7 to 9. However, in another embodiment the film is oriented to the same extent in both the MD and TD directions.

The films may vary in thickness depending on the intended application; however, films of a thickness from 1 to 50 μm are usually suitable. Films intended for packaging are usually from 10 to 50 μm thick. The thickness of the sealing layer is typically 0.2 to 50 μm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.

In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In a preferred embodiment, one or both of the surface layers is modified by corona treatment.

In another embodiment, this invention relates to:

-   1. A catalyst system comprising the reaction product of fluorided     silica support, alkylalumoxane activator and at least two     metallocene catalyst compounds, where the first metallocene is a     bridged monocyclopentadienyl group 4 transition metal compound and     the second metallocene is a biscyclopentadientyl group 4 transition     metal compound where the fluorided silica support has not been     calcined at a temperature of 400° C. or more. -   2. The catalyst system of paragraph 1, wherein the metallocenes are     represented by the formula:

T_(y)Cp_(m)MG_(n)X_(q)

wherein each Cp is, independently, a cyclopentadienyl group which may be substituted or unsubstituted, M is a group 4 transition metal, G is a heteroatom group represented by the formula JR*_(Z) where J is N, P, O or S, and R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms and z is 1 or 2, T is a bridging group, and y is 0 or 1, X is a leaving group, and m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal; wherein m=1, n=1 and y=1 in the first metallocene catalyst compound; and n=0 and m=2 in the second metallocene catalyst compound.

-   3. The catalyst system of paragraph 2, wherein y is one in the     second metallocene compound and at least one Cp in the second     metallocene compound is not a substituted or unsubstituted indene     group. -   4. The catalyst system of paragraph 2, wherein each Cp is a     cyclopentadiene, indene or fluorene, which may be substituted or     unsubstituted, each M is titanium, zirconium, or hafnium, and each X     is, independently, a halide, a hydride, an alkyl group, an alkenyl     group or an arylalkyl group. -   5. The catalyst system of paragraph 1, wherein the activator     comprises an alkylalumoxane and a non-coordinating anion. -   6. The catalyst system of paragraph 1, wherein the activator     comprises methylalumoxane. -   7. The catalyst system of paragraph 1, wherein for the bridged     monocyclopentadienyl transition metal compound m is one, n is one,     where J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl,     heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl,     dodecyl, adamantyl or an isomer thereof. -   8. The catalyst system of paragraph 1, wherein the bridged     monocyclopentadienyl transition metal compound comprises one or more     of: -   dimethylsilyl     (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl; -   dimethylsilyl     (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride; -   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium     dimethyl; -   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium     dichloride; -   μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂; -   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)₂; -   μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)₂; -   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂; -   μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂; -   μ-(CH₃)₂Si(η⁵-2.6.6-trimethyl-1.5.6.7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M(R)₂; -   where M is selected from a group consisting of Ti, Zr, and Hf and R     is selected from halogen or C₁ to C₅ alkyl. -   9. The catalyst system of paragraph 1, wherein the second     metallocene compound comprises one or more of:     Bis(tetrahydroindenyl)Hf Me₂;     Bis(1-butyl,3-methylcyclopentadienyl)ZrCl₂;     Bis-(n-butylcyclopentadienyl)ZrCl₂; (Dimethylsilyl)₂O     bis(indenyl)ZrCl₂;     Dimethylsilyl(3-(3-methylbutyl)cyclopentadienyl)(2,3,4,5-tetramethylcyclopentadienyl)ZrCl₂;     Dimethylsilylbis(tetrahydroindenyl)ZrCl₂;     Dimethylsilyl-(3-phenyl-indenyl)(tetramethylcyclopentadienyl)ZrCl₂;     Dimethylsilyl(3-neopentylcyclopentadienyl)(tetramethylcyclopentadienyl)HfCl₂;     Tetramethyldisilylene bis(4-(3,5-di-tert-butylphenyl)-indenyl)ZrCl₂;     Cyclopentadienyl(1,3-diphenylcyclopentadienyl)ZrCl₂;     bis(cyclopentadienyl)zirconium dichloride;     bis(pentamethylcyclopentadienyl)zirconium dichloride;     bis(pentamethylcyclopentadienyl)zirconium dimethyl;     is(pentamethylcyclopentadienyl)hafnium dichloride;     bis(pentaniethylcyclopentadienyl)zirconium dimethyl;     bis(1-methyl-3-n-butylcyelopentadienyl)zirconium dichloride;     bis(1-methyl-3-n-butylcyclopentadienvl)zirconium dimethyl;     bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride;     bis(1-methyl-3-n-butyleyclopentadienyl)zirconium dimethyl;     bis(indenyl)zirconium dichloride; bis(indenyl)zirconium dimethyl;     bis(tetrahydro-1-indenyl)zirconium dichloride;     bis(tetrahydro-1-indenyl)zirconium dimethyl;     dimethylsilylbis(tetrahydroindenyl)zirconium dichloride;     dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl;     dimethylsilylbis(indenyl)zirconium dichloride;     dimethylsilyl(bisindenyl)zirconium dimethyl;     dimethylsilylbis(cyclopentadienyl)zirconium dichloride; and     dimethylsilylbis(eyclopentadienyl)zirconium dimethyl. -   10. The catalyst system of paragraph 1, wherein the first and second     metallocene compounds comprise one or more of: -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and bis(1-Bu,3-Me-Cp) ZrCl₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂) bis(indenyl)ZrCl₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrCl₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrMe₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and SiMe₂(3-neopentylCp)((Me₄Cp)HfCl₂; -   SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and     SiMe₂(3-neopentylcyclopentadienyl)(Me₄Cp)HfMe₂; -   SiMe₂(Me₄Cp)(1-adamantylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂; and -   SiMe₂(Me₄Cp)(1-t-butylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂. -   11. The catalyst system of paragraph 1, wherein the flourided     support has been calcined at a temperature of 100° C. to less than     400° C. -   12. A process to produce ethylene polymer comprising: i) contacting,     in the gas phase or slurry phase, ethylene and, optionally C₃ to C₂₀     comonomer, with the catalyst system of any of paragraphs 1 to 11,     and ii) obtaining an ethylene polymer comprising at least 50 mol %     ethylene. -   13. The process of paragraph 12, wherein the ethylene polymer     comprises ethylene and at least one C₃ to C₂₀ comonomer, and has a     bi-modal composition distribution. -   14. The process of paragraph 13, wherein the ethylene polymer has a     multimodal molecular weight distribution as determined by Gel     Permeation Chromotography. -   15. The method of paragraph 12, wherein the activator comprises     methylalumoxane. -   16. The method of paragraph 20, wherein the activator further     comprises a non-coordinating anion activator. -   17. The method of paragraph 12, wherein the process occurs at a     temperature of from about 0° C. to about 300° C., at a pressure in     the range of from about 0.35 MPa to about 10 MPa, and at a time up     to 300 minutes. -   18. The method of paragraph 12, wherein the comonomer is present and     is selected from propylene, butene, pentene, hexene, heptene,     octene, nonene, decene, undecene, dodecene or a mixtures thereof. -   19. The process of paragraph 12, wherein the flourided supported     catalyst systems is prepared by the method comprising combining a     fluoride compound with non-polar solvent (such as water), then     combining with a slurry of non-polar solvent and support, removing     the non-polar solvent, thereafter combining the calcined support     with a second solvent, which may be the same as or different from     the non-polar solvent, and two catalyst compounds and activator,     wherein the flourided support is calcined at a temperature from 100     to less than 400° C., before or after combination with the activator     and/or catalyst compounds. -   20. The method of paragraph 19, wherein the ratio (by weight) of     non-polar solvent to non-polar solvent is between 1:10 to 1:1000. -   21. The method of paragraph 20, wherein the non-polar solvent is     toluene, pentane, hexane, benzene, or chloroform. -   22. The method of paragraph 19, wherein the fluoride compound is one     or more of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄,     (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆, GaF₃,     SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅, IF₂, NF₃, HF, BF₃, NHF₂ and     NH₄HF₂. -   23. The method of paragraph 21, wherein the fluoride compound     comprises ammonium hexafluorosilicate, ammonium tetrafluoroborate or     a mixture thereof. -   24. The method of paragraph 19, wherein the non-polar solvent is     water, the ratio (by weight) of water to non-polar solvent is     between 1:10 to 1:1000; the non-polar solvent is toluene, pentane,     hexane, benzene, or chloroform; and the fluoride compound is one or     more of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄,     (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆, GaF₃,     SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅, IF₇, NF₃, HF, BF₃, NHF₂ and     NH₄HF₂. -   25. A method of preparing fluorided supported catalyst systems     comprising combining a fluoride compound with water, then combining     with a slurry of non-polar solvent and support, removing the     non-polar solvent, thereafter combining the calcined support with a     second solvent, which may be the same or different from the     non-polar solvent, and two catalyst compounds and alkylalumoxane     activator, wherein the fluorided support is calcined at a     temperature from 100 to less than 400° C., before or after     combination with the activator and/or catalyst compounds.

Experimental

Room temperature is 23° C. unless otherwise noted.

MAO is methyl alumoxane (30 wt % in toluene) obtained from Albemarle.

Gel Permeation Chromotography With Three Detectors (GPC-3D)

Mw, Mn and Mw/Mn are determined by using a High Temperature Gel Permeation Chromatography (Agilent PL-220), equipped with three in-line detectors, a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer. Experimental details, including detector calibration, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) and references therein. Three Agilent PLgel 10 μm Mixed-B LS columns are used. The nominal flow rate is 0.5 mL/min, and the nominal injection volume is 300 μL. The various transfer lines, columns, viscometer and differential refractometer (the DRI detector) are contained in an oven maintained at 145° C. Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.1 μm Teflon filter. The TCB is then degassed with an online degasser before entering the GPC-3D. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160° C. with continuous shaking for about 2 hours. All quantities are measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.284 g/ml at 145° C. The injection concentration is from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. Prior to running each sample the DRI detector and the viscometer are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 hours before injecting the first sample. The LS laser is turned on at least 1 to 1.5 hours before running the samples. The concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, I_(DRI), using the following equation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 145° C. and λ=690 nm. Units on parameters throughout this description of the GPC-3D method are such that concentration is expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature DAWN HELEOS. The molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):

$\frac{K_{o}c}{\Delta \; R\; (\theta)} = {\frac{1}{{MP}(\theta)} + {2\; A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the DRI analysis, A₂ is the second virial coefficient. P(θ) is the form factor for a monodisperse random coil, and K_(o) is the optical constant for the system.

$K_{o} = \frac{4\; \pi^{2}\; {n^{2}\left( {{dn}/{dc}} \right)}}{\lambda^{4}N_{A}}$

where N_(A) is Avogadro's number, and (dn/dc) is the refractive index increment for the system, which take the same value as the one obtained from DRI method. The refractive index, n=1.500 for TCB at 145° C. and λ=657 nm.

A high temperature Viscotek Corporation viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, η_(s), for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the following equation:

η_(s) =c[η]+0.3(c[η])²

where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of the GPC-DRI-LS-VIS method as follows. The average intrinsic viscosity, [η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromatographic slices, i, between the integration limits. The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

M_(v) is the viscosity-average molecular weight based on molecular weights determined by LS analysis. Z average branching index (g′_(Zave)) is calculated using Ci=polymer concentration in the slice i in the polymer peak times the mass of the slice squared, Mi².

All molecular weights are weight average unless otherwise noted. All molecular weights are reported in g/mol unless otherwise noted.

Molecular Weight and Comonomer Composition Determination With PolymerChar GPC-IR

The distribution and the moments of molecular weight (Mw, Mn, Mw/Mn, etc.) and the comonomer content (C2, C3, C6, etc.), are determined with a high temperature Gel Permeation Chromatography (PolymerChar GPC-IR) equipped with a multiple-channel band filter based Infrared detector ensemble IR5, in which a broad-band channel is used to measure the polymer concentration while two narrow-band channels are used for characterizing composition. Three Agilent PLgel 10 μm Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxy toluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1 μmTeflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow rate is 1.0 mL/min and the nominal injection volume is 200 μL. The whole system including transfer lines, columns, detectors are contained in an oven maintained at 145° C. Given amount of polymer sample is weighed and sealed in a standard vial with 10 μL flow marker (Heptane) added to it. After loading the vial in the autosampler, polymer is automatically dissolved in the instrument with 8 mL added TCB solvent. The polymer is dissolved at 160° C. with continuous shaking for about 1 hour for most PE samples or 2 hour for PP samples. The TCB densities used in concentration calculation are 1.463 g/ml at room temperature and 1.284 g/ml at 145° C. The sample solution concentration is from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.

The concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal, I, using the following equation:

c=αI

where α is the mass constant determined with PE or PP standards. The mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume.

The molecular weight is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards. The MW is calculated at each elution volume with following equation.

${\log \; M_{X}} = {\frac{\log \; \left( {K_{X}/K_{PS}} \right)}{a_{X} + 1} + {\frac{a_{PS} + 1}{a_{X} + 1}\log \; M_{PS}}}$

where the variables with subscript “X” stand for the test sample while those with subscript “PS” stand for PS. In this method, a_(PS)=0.67 and K_(PS)=0.000175 while a_(X) and K_(X) are obtained from published literature. Specifically, a/K=0.695/0.000579 for PE and 0.705/0.0002288 for PP.

The comonomer composition is determined by the ratio of the IR detector intensity corresponding to CH₂ and CH₃ channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR.

CRC was performed according to the following procedure: Cross-fractionation chromatography (CFC) analysis was done using a CFC-2 instrument from Polymer Char, S.A., Valencia, Spain. The principles of CFC analysis and a general description of the particular apparatus used are given in the article Ortin, A.; Monrabal, B.; Sancho-Tello, J. Macromol. Symp. 2007, 257, 13. FIG. 1 of the article is an appropriate schematic of the particular apparatus used. Pertinent details of the analysis method and features of the apparatus used are as follows.

1,2-Dichlorobenzene (ODCB) solvent stabilized with approximately 380 ppm of 2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxy toluene) was used for preparing the sample solution and for elution. The sample to be analyzed (approximately 50 mg) was dissolved in ODCB (25 ml metered at ambient temperature) by stirring (200 rpm) at 150° C. for 75 min. A small volume (0.5 ml) of the solution was introduced into a TREF column (stainless steel; o.d., ⅜″; length, 15 cm; packing, non-porous stainless steel micro-balls) at 150° C., and the column temperature was stabilized for 30 min at a temperature (120-125° C.) approximately 20° C. higher than the highest-temperature fraction for which the GPC analysis was included in obtaining the final bivariate distribution. The sample volume was then allowed to crystallize in the column by reducing the temperature to 30° C. at a cooling rate of 0.2° C./min. The low temperature was held for 10 min before injecting the solvent flow (1 ml/min) into the TREF column to elute the soluble fraction (SF) into the GPC columns (3× PLgel 10 μm Mixed-B 300×7.5 mm, Varian, Inc.); the GPC oven was held at high temperature (140° C.). The SF was eluted for 5 min from the TREF column and then the injection valve was put in the “load” position for 40 min to completely elute all of the SF through the GPC columns (standard GPC injections). All subsequent higher-temperature fractions were analyzed using overlapped GPC injections wherein at each temperature step the polymer was allowed to dissolve for at least 16 min and then injected from the TREF column into the GPC column for 3 min. The IR4 (Polymer Char) infrared detector was used to generate an absorbance signal that is proportional to the concentration of polymer in the eluting flow.

The universal calibration method was used for determining the molecular weight distribution (MWD) and molecular-weight averages (Mn, Mw, etc.) of eluting polymer fractions. Thirteen narrow molecular-weight distribution polystyrene standards (obtained from Polymer Labs, UK) within the range of 1.5-8200 kg/mol were used to generate a universal calibration curve. Mark-Houwink parameters were obtained from Appendix I of Mori, S.; Barth, H. G. Size Exclusion Chromatography; Springer, 1999. For polystyrene K=1.38×10-4 dl/g and α=0.7; and for polyethylene K=5.05×10-4 dl/g and α=0.693 were used. For a polymer fraction, which eluted at a temperature step, that has a weight fraction (weight % recovery) of less than 0.5 %, the MWD and the molecular-weight averages were not computed; additionally, such polymer fractions were not included in computing the MWD and the molecular-weight averages of aggregates of fractions.

EXAMPLE 1 Preparation of Fluorided Silica-1 Via Dry Mixing.

50 g of Grace Davison D948™ silica and 2.3 g (NH₄)₂SiF₆ were combined in a plastic jar. The mixture was tumbled together for 1 hour. The solid mixture was transferred into a tube furnace, and was heated to 200° C. under constant nitrogen flow (temperature program: 25° C./h ramped to 150° C; held at 150° C. for 4 hours; 50° C./h ramped to 200° C; held at 200° C. for 4 hours; cooled down to room temperature). 47 g of flourided silica-1 was collected after the calcination.

Preparation of Fluorided Silica-2 Via Wet Mixing:

1.18 g (NH₄)₂SiF₆ was dissolved in 7.00 g water in a 20 ml glass vial. 50 g of Grace Davison D948™ silica and 200 g of toluene were combined in a 250 ml Wheaton Celstir™. Under vigorous stirring, the aqueous stock solution of (NH₄)₂SiF₆ was added via a syringe to the toluene slurry of silica. The mixture was allowed to stir at room temperature for 2.5 h. The slurry was filtered through a 110 ml Optichem™ disposable polyethylene frit, rinsed with 200 g pentane three times, then dried in air overnight to yield a white, free-flowing solid. The solid was transferred into a tube furnace, and was heated under constant nitrogen flow (temperature program: 25° C./h ramped to 150° C; held at 150° C. for 4 hours; 50° C./h ramped to 200° C; held at 200° C. for 4 hours; cooled down to room temperature). 46 g of flourided silica-2 was collected after the calcination. The calculated “F” loading was 0.9 mmol/g.

Preparation of Supported Methylalumoxane (sMAQ) From Flourided Silica-1.

In a drybox, 36 g MAO toluene solution (Albermarle, 13.6 wt % Al) and 68 g of anhydrous toluene were combined in a 125 ml Wheaton Celstir™. The stirring rate was set to 450 rpm. Every 5 minutes, 5 g of flourided silica-1 was slowly added to the Celstir™. A total amount of 26 g of flourided silica-1 was added over a period of 30 minutes. The resulting slurry was allowed to stir at room temperature for 15 minutes. Then the Celstir™ was placed in a sand bath heated to 100° C. The slurry was heated at 100° C. for an additional 3 hours at a stirring rate of 215 rpm. The final slurry was filtered through a 110 ml Optichem disposable polyethylene frit. The solid collected in the frit was first rinsed with 30 g toluene for 2 times, then 30 g pentane for 3 times. The solid was dried in-vacuo for 3 hours. 34.9 g of sMAO-1 was obtained. Calculated Al loading: 4.2 mmol Al per gram of sMAO-1.

Preparation of Supported Methylalumoxane (sMAQ) from Flourided Silica-2.

In a drybox, 34.5 g MAO toluene solution (Albermarle, 13.6 wt % Al) and 100 g of anhydrous toluene were combined in a 250 ml Wheaton Celstir™. The stir rate was set to 450 rpm. Every 5 minutes, 5 g of fluorided silica-2 was slowly added to the Celstir™. A total amount of 27.6 g of fluorided silica-2 was added over a period of 30 minutes. The resulting slurry was allowed to stir at room temperature for 15 minutes. Then the Celstir™ was placed in a sand bath heated to 100° C. The slurry was heated at 100° C. for an additional 3 hours at a stirring rate of 215 rpm. The final slurry was filtered through a 110 ml Optichem disposable polyethylene frit. The solid collected in the frit was first rinsed with 80 g toluene for 2 times, then 60 g pentane for 3 times. The solid was dried in-vacuo for 12 hours. 37.4 g of free-flowing sMAO-2 was obtained. The calculated Al loading was 4.4 mmol Al per gram of sMAO-2.

Comparison of Physical Properties of Fluorided Supports

Particle size Surface Pore Pore Distribution** Area* volume* Diameter* Mean Support (m²/g) (cm³/g) (Å) (μm) S.D. (μm) Silica-1 241 1.68 280 60.28 18.28 Silica-2 231 1.57 271 59.11 21.10 sMAO-1 353 0.96 109 58.21 18.23 sMAO-2 377 1.00 104 52.41 21.38 *BET surface area and porosity analysis were carried out with ASAP 2420 Accelerated Surface Area and Porosimetry Systems from Micromeritics. **Particle size distribution (PSD) was measured with LS 13 320 Laser Diffraction Particle Size Analyzer.

Chemical Properties of Fluorided Supports.

The chemical composition of fluorided silica supports was studied by NMR experiments. A representative procedure is as follows: In a 20 ml glass vial in the drybox, combined 0.203 g silica-2, 26.5 mg NMR internal standard Bis(4-fluorophenyl)methane (0.13 mmol), 0.80 g MAO/toluene solution (30 wt %, Albemarle) and 0.20 g of toluene. The mixture was vortexed at room temperature for 90 min and was allowed to sit still for 20 min. A small sample of the supernatant liquid was dissolved in THF-d8 in an NMR tube and the 1H NMR spectrum was taken on Bruker 400 MHz NMR spectrometer (FIG. 9).

An important difference noted between the middle spectrum in FIG. 9 (from reaction with silica-1) and bottom spectrum in FIG. 9 (from reaction with silica-2) is the presence of trimethylsilane (TMS), which originated from the reaction between the fluorinating agent (NH₄)₂SiF₆ and MAO (see top spectrum in FIG. 9 for reference). This observation suggests the presence of residual (NH₄)₂SiF₆ (estimated to be greater than 0.05 mmol (NH₄)₂SiF₆ per gram based on NMR integration) in fluorided silica-1 prepared through the dry-mixing method. Fluorided silica-2 prepared through the wet-mixing method contains no detectable amount of residual (NH₄)₂SiF₆.

The significance of this observation is two-fold. First, the improved fluorided silica preparation (e.g., silica-2, wet-mixing) can be chemically differentiated from silica-1, dry-mixed materials (such as those described in U.S. Publication No. 2002/0123582). Secondly, since there are no residual fluorinating agents in silica-2, the possibility of in-situ generation of fluorinated MAO with fluorinating agent (organic or inorganic fluorine-containing compounds, as described in U.S. Pat. No. 7,355,058) can be ruled out in the preparation of sMAO-2.

Synthesis of Catalysts

Catalyst A was synthesized according to preparation described in patent WO 93/19103. Catalyst B was purchased from Boulder and used as received. Catalyst D was synthesized according to U.S. Pat. No. 7,141,632.

Synthesis of Catalyst C:

Lithium salt of indene: Indene (25.1 g, 0.216 mol, 1.0 equiv.) was dissolved in 250 ml pentane in a 500 ml round bottom flask. Hexyl lithium/toluene solution (2.30 mol/L, 94 ml, 0.216 mol, 1.0 equiv.) was added to the flask via a syringe. The mixture was allowed to stir at room temperature for 16 h. The mixture was filtered and the collected white fine solid was washed with 50 ml pentane for 3 times. After drying in vacuo for 1 h, 26.0 g lithium salt was obtained (98% yield).

1-Propyl indene: In a 100 ml round bottom flask kept at −30° C. was added 1-iodopropane (6.80 g, 40 mmol, 1.0 equiv.) and 50 ml ether. Indene lithium salt (5.368 g, 44 mmol, 1.1 equiv.) was added to the flask in portion. The reaction mixture was stirred at −30° C. for 30 min, then was brought to room temperature to stir for another 16 h. The solvent was removed in vacuo. 35 ml pentane was added to the residue to extract the product. A pale yellow oil was obtained after removing pentane in vacuo (5.0 g, 79% yield).

Lithium salt of 1-propyl indene: In a 100 ml round bottom flask chilled to −30° C. was added 1-propyl indene (5.0 g, 31.6 mmol, 1.0 equiv.) and 50 ml ether. Dropwisely added n-butyl lithium/hexane solution (2.62 mol/L, 12.06 ml, 31.6 mmol, 1.0 equiv.) via a syringe. The mixture was stirred at −30° C. for 20 min then warmed up to room temperature. The solvent was removed in vacuo. The solid was washed with 20 ml pentane for 2 times, and was dried in vacuo. White solid was obtained (4.59 g, 88% yield).

Catalyst C: In a 250 ml round bottom flask chilled to −30° C. combined 1-propyl indene lithium salt (6.378 g, 38.9 mmol, 2.0 equiv.) and 100 ml ether. ZrCl₄(Et₂O)₂ (7.417 g, 19.5 mmol, 1.0 equiv.) was added to the flask in portion. The mixture was stirred at −30° C. for 20 min then warmed up to room temperature for 30 min. The solvent was removed in vacuo. To the solid residue was added dichloromethane (30 ml). The resulting slurry was filtered through Celite™ to yield a red solution. The dichloromethane solvent was then removed in vacuo to yield an orange solid. The solid was washed with 5 ml pentane for 3 times, and then dried in vacuo for 2 h. Final product is orange/yellow solid (6.81 g, 73% yield).

Synthesis of Catalyst E:

All reactions in the synthesis of Catalyst E were carried out in the dry-box under nitrogen atmosphere. 5-isopentylcyclopenta-1,3-diene (1): 1-bromo-3-methylbutane (7.93 mL, 10,000 g, 66.21 mmol, 1.00 eq) was added to cyclopenta-2,4-dienylmagnesium chloride (93.38 mL of 0.934M sIn., 88.06 mmol, 1.33 eq) in a 500 mL round bottom flask and stirred at 60° C. for 4 hours. The mixture was brought to room temperature and concentrated under a stream of nitrogen. Pentane was added and the suspension was put under vacuum to remove the pentane and any remaining THF. The resulting residue was taken up in pentane and the solid impurities removed via vacuum filtration. The filtrate was concentrated to give light yellow oil, 1 (8.12 g, 59.60 mmol, 90.02%yield). Used in synthesis of 2 without further analysis.

Lithium salt of 5-isopentylcyclopenta-1,3-diene (2): Immediately following removal of the solvent, the 5-isopentylcyclopenta-1,3-diene, 1, (8.12 g, 59.60 mmol, 1.00 eq) was taken up in tetrahydrofuran (100 mL). n-Butyllithium (25.0 mL of a2.5M sIn., 59.60 mmol, 1.00 eq) was added to the stirring solution and the reaction was allowed to stir at room temperature overnight. The solvent was removed under nitrogen and pentane was added to slurry up the solid. The white solid, 2, was collected via vacuum filtration and rinsed with additional pentane. Residual solvent was removed under vacuum giving 4.513 g (31.74 mmol, 53.25% yield) of the white solid, 2.

(3-isopentylcyclopenta-2,4-dienyl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dienyl)silane (3): Chlorodimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dienyl)silane (6.818 g, 18.58 mmol, 1.00 eq) was added to 2 in 20 mL of tetrahydrofuran. The reaction mixture was stirred overnight at room temperature. Pentane was added and solvent was removed under vacuum. The residue was taken up into pentane, filtered through Celite™ then removed solvent under reduced pressure. This gave yellow oil, 3, (6.430 g, 20.44 mmol, 64.40% yield).

Lithium salt of (3-isopentylcyclopenta-2,4-dienyl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dienyl)silane (4): n-Butyllithium (17.2 mL of a 2.5M sIn., 42.92 mmol, 2.1 eq) was added drop-wise to a solution of 3 in 100 mL of tetrahydrofuran. The reaction was stirred 24 h at room temperature. The mixture was concentrated under a stream of nitrogen. Pentane was added and solvents were removed in vacuo. The residue was slurried up in pentane and the solid was collected via vacuum filtration giving white solid, 4 (3.832 g, 11.73 mmol, 57.4%).

Catalyst E: Hafnium tetrachloride-bis-etherate (5.49 g, 11.73 mmol, 1.00 eq) was added to 4 (3.832 g, 11.73 mmol, 1.00 eq) in 100 mL of tetrahydrofuran/diethyl ether (1:1 ) at −35° C. The solution was stirred overnight at room temperature. The mixture was concentrated under a stream of nitrogen and pentane was added and solvents removed in vacuo. The residue was taken up in pentane and filtered through Celite™. The filtrate was concentrated in vacuo giving yellow oil, Catalyst E (5.633 g, 5.05 mmol, 43.1%).

Preparation of Supported Dual-Metallocene Catalyst Systems.

Supported catalyst a-1: In a 20 ml glass vial in a dry box was added 1 g of the sMAO-1 obtained above. 3 g Toluene was added to the vial, followed by 1 g toluene solution containing Catalyst A (35 μmol) and Catalyst B (6 μmol). The vial was fitted with a cap and then vortexed at room temperature for 90 min. The resulting slurry was filtered through a 25 ml Optichem disposable polyethylene frit and rinsed with 3 g toluene for 2 times and 3 g pentane for 3 times. The supported catalyst was dried in-vacuo. 0.997 g of supported catalyst a-1 (Catalyst A/Catalyst B ratio=5.8) was obtained.

Supported catalyst b-1: In a 20 ml glass vial in the dry box was added 1 g sMAO-1 obtained above. 3 g Toluene was added to the vial, followed by 1 g toluene solution containing metallocene Catalyst A (35 μmol) and Catalyst C (6 μmol). The vial was fitted with a cap and then vortexed at room temperature for 90 min. The resulting slurry was filtered through a 25 ml Optichem disposable polyethylene frit and rinsed with 3 g toluene for 2 times and 3 g pentane for 3 times. The supported catalyst was dried in-vacuo. 0.997 g of supported catalyst b-1 (Catalyst A/Catalyst C ratio=5.8) was obtained.

Supported catalyst c-1: In a 20 ml glass vial in the dry box was added 1 g sMAO-1 obtained above. 3 g Toluene was added to the vial, followed by 1 g toluene solution containing metallocene Catalyst A (29 μmol) and Catalyst D (9 μmol). The vial was fitted with a cap and then vortexed at room temperature for 90 min. The resulting slurry was filtered through a 25 ml Optichem disposable polyethylene frit and rinsed with 3 g toluene for 2 times and 3 g pentane for 3 times. The supported catalyst was dried in-vacuo. 1.001 g of supported catalyst c-1 (Catalyst A/Catalyst D ratio=3.2) was obtained.

Supported catalyst d-1: In a 20 ml glass vial in the dry box was added 1 g sMAO-1 obtained above. 3 g Toluene was added to the vial, followed by 1 g toluene solution containing metallocene Catalyst C (35 μmol) and Catalyst E (6 μmol). The vial was fitted with a cap and then vortexed at room temperature for 90 min. The resulting slurry was filtered through a 25 ml Optichem disposable polyethylene frit and rinsed with 3 g toluene for 2 times and 3 g pentane for 3 times. The supported catalyst was dried in-vacuo. 1.001 g of supported catalyst d-1 (Catalyst A/Catalyst E ratio=5.8) was obtained.

Supported catalyst e-1: In a dry box, 44.1 g sMAO-1 and 120 g anhydrous toluene were combined in a 250 ml Wheaton Celstir™. The stir rate was set to 450 rpm. A 60 g toluene stock solution containing Catalyst A (1.29 mmol) and Catalyst B (0.44 mmol) was added to the Celstir™ dropwisely with a pipette. The resulting yellow-orange slurry was allowed to stir at room temperature for 60 min. The resulting slurry was filtered through a 110 ml Optichem disposable polyethylene frit, and rinsed with 60 g toluene for 2 times, followed by 45 g pentane for 3 times. The orange solid was dried in-vacuo for 12 hours. 43.9 g of supported catalyst 6 was obtained (Catalyst A/Catalyst B mole ratio=2.9).

Supported catalyst e-2: In a dry box, 51.7 g MAO toluene solution (Albermarle, 13.6 wt % Al) and 160 g anhydrous toluene were combined in a 250 ml Wheaton Celstir™. The stir rate was set to 450 rpm. Every 5 minutes, 5 g of fluorided silica-2 was slowly added to the Celstir™. A total amount of 40.5 g of fluorided silica-2 was added over a period of 40 minutes. The resulting slurry was allowed to stir at room temperature for 15 minutes. Then the Celstir™ was placed in a sand bath heated to 100° C. The slurry was heated at 100° C. for an additional 3 hours at a stirring rate of 200 rpm. The final slurry was filtered through a 110 ml Optichem disposable polyethylene frit. The solid collected in the frit was first rinsed with 80 g toluene for 2 times. The collected solid was transferred back to the Celstir™ and slurried with 120 g anhydrous toluene. Set stir rate to 450 rpm. A 60 g toluene stock solution containing Catalyst A (1.56 mmol) and Catalyst B (0.52 mmol) was added to the Celstir™ dropwisely with a pipette. The resulting yellow-orange slurry was allowed to stir at room temperature for 60 min. The resulting slurry was filtered through a 110 ml Optichem disposable polyethylene frit, and rinsed with 80 g toluene for 2 times, followed by 60 g pentane for 3 times. The orange solid was dried in-vacuo for 12 hours. 56.1 g of supported catalyst e-2 was obtained (Catalyst A/Catalyst B mole ratio=3).

Supported catalyst f-1: In a dry box, 40.3 g MAO toluene solution (Albermarle, 13.6 wt % Al) and 70 g anhydrous toluene were combined in a 250 ml Wheaton Celstir™. The stir rate was set to 450 rpm. Every 5 minutes, 5 g of fluorided silica-1 was slowly added to the Celstir™. A total amount of 28.9 g of fluorided silica-1 was added over a period of 30 minutes. The resulting slurry was allowed to stir at room temperature for 15 minutes. Then the Celstir™ was placed in a sand bath heated to 80° C. The slurry was heated at 80° C. for an additional 3 hours at a stirring rate of 200 rpm. The final slurry was filtered through a 110 ml Optichem disposable polyethylene frit. The solid collected in the frit was first rinsed with 30 g toluene for 3 times. The collected solid was transferred back to the Celstir™ and slurried with 50 g anhydrous toluene. Set stir rate to 450 rpm. A 70 g toluene stock solution containing Catalyst A (1.44 mmol) and Catalyst B (0.24 mmol) was added to the Celstir™ dropwisely with a pipette. The resulting yellow-orange slurry was allowed to stir at room temperature for 60 min. The resulting slurry was filtered through a 110 ml Optichem disposable polyethylene frit, and rinsed with 30 g toluene for 2 times, followed by 30 g pentane for 3 times. The orange solid was dried in-vacuo for 1 hour. 40.4 g of supported catalyst f-1 was obtained (Catalyst A/Catalyst B mole ratio=6).

Supported catalyst g-2: In a dry box, 50.0 g MAO toluene solution (Albermarle, 13.6 wt % Al) and 160 g anhydrous toluene were combined in a 250 ml Wheaton Celstir™. The stir rate was set to 450 rpm. Every 5 minutes, 5 g of fluorided silica-2 was slowly added to the Celstir™. A total amount of 40.1 g of fluorided silica-2 was added over a period of 40 minutes. The resulting slurry was allowed to stir at room temperature for 35 minutes. Then the Celstir™ was placed in a sand bath heated to 100° C. The slurry was heated at 100° C. for an additional 3 hours at a stirring rate of 230 rpm. The final slurry was filtered through a 110 ml Optichem disposable polyethylene frit. The solid collected in the frit was first rinsed with 80 g toluene for 2 times. The collected solid was transferred back to the Celstir™ and slurried with 120 g anhydrous toluene. Set stir rate to 450 rpm. A 65 g toluene stock solution containing Catalyst A (1.96 mmol) and Catalyst B (0.17 mmol) was added to the Celstir™ dropwisely with a pipette. The resulting yellow-orange slurry was allowed to stir at room temperature for 80 min. The resulting slurry was filtered through a 110 ml Optichem disposable polyethylene frit, and rinsed with 80 g toluene for 2 times, followed by 70 g pentane for 3 times. The orange solid was dried in-vacuo for 3 hours. 57.0 g of supported catalyst g-2 was obtained (Catalyst A/Catalyst B mole ratio=12).

Supported catalyst h-1: In a dry box, 34.2 g sMAO-1 obtained above was weighed into a 125 ml Wheaton Celstir™. 70 g of toluene was added to the Celstir™. The stir rate was set to 450 rpm. 70 g toluene stock solution containing Catalyst A (1.69 mmol) and Catalyst C (0.60 mmol) was added to the Celstir™ dropwisely with a pipette. The resulting yellow-orange slurry was allowed to stir at room temperature for 90 min. The resulting slurry was filtered through a 110 ml Optichem disposable polyethylene frit, and rinsed with 30 g toluene for 2 times, followed by 30 g pentane for 3 times. The orange solid was dried in-vacuo for 3 hours (Catalyst A/Catalyst C ratio=2.8).

Supported catalyst h-2: In the dry box, 47.5 g sMAO-2 and 150 ml anhydrous toluene were combined in a 250 ml Celstir™. The stir rate was set to 450 rpm. A 60 ml toluene stock solution containing Catalyst A (1.43 mmol) and Catalyst C (0.48 mmol) was added to the Celstir™ dropwisely with a pipette. The resulting yellow-orange slurry was allowed to stir at room temperature for 60 min. The resulting slurry was filtered through a frit, and rinsed with 60 g toluene for 2 times, followed by 45 g pentane for 3 times. The orange solid was dried in vacuo for 12 hours. 47.7 g of supported catalyst was obtained (Catalyst A/Catalyst C ratio=3.0).

Supported catalyst i-1: In a 20 ml glass vial in the dry box was added 1 g sMAO-2. 3 g Toluene was added to the vial, followed by 1 g toluene solution containing Catalyst B (40 μmol). The vial was fitted with a cap and then vortexed at room temperature for 90 min. The resulting slurry was filtered through a 25 ml Optichem disposable polyethylene frit and rinsed with 3 g toluene for 2 times and 3 g pentane for 3 times. The supported catalyst was dried in-vacuo.

Supported catalyst i-2: In a 20 ml glass vial in the dry box was added 1 g sMAO-2. 3 g Toluene was added to the vial, followed by 1 g toluene solution containing Catalyst B (40 μmol). The vial was fitted with a cap and then vortexed at room temperature for 90 min. The resulting slurry was filtered through a 25 ml Optichem disposable polyethylene frit and rinsed with 3 g toluene for 2 times and 3 g pentane for 3 times. The supported catalyst was dried in-vacuo.

Supported catalyst j-1: In a 20 ml glass vial in the dry box was added 1 g sMAO-1. 3 g Toluene was added to the vial, followed by 1 g toluene solution containing Catalyst A (40 μmol). The vial was fitted with a cap and then vortexed at room temperature for 90 min. The resulting slurry was filtered through a 25 ml Optichem disposable polyethylene frit and rinsed with 3 g toluene for 2 times and 3 g pentane for 3 times. The supported catalyst was dried in-vacuo.

Supported catalyst j-2: In a 20 ml glass vial in the dry box was added 1 g sMAO-2. 3 g Toluene was added to the vial, followed by 1 g toluene solution containing Catalyst A (40 μmol). The vial was fitted with a cap and then vortexed at room temperature for 90 min. The resulting slurry was filtered through a 25 ml Optichem disposable polyethylene frit and rinsed with 3 g toluene for 2 times and 3 g pentane for 3 times. The supported catalyst was dried in-vacuo.

EXAMPLE 2 High Throughput Ethylene-1-Hexene Copolymerization

Supported catalysts a-1 to d-1 were tested in a high throughput unit in slurry ethylene-1-hexene copolymerization.

Preparation of catalyst slurry for high throughput run: In a dry box, 45 mg of supported catalyst was weighed into a 20 ml glass vial. 15 ml of toluene was added to the vial to make a slurry that contained 3 mg supported catalyst/ml slurry. The resulting mixture was vortexed prior to injection.

High Throughput—Polymerizations:

Transition metal compounds were supported as detailed in the examples above. Solvents, polymerization grade toluene and isohexane were supplied by ExxonMobil Chemical Company and thoroughly dried and degassed prior to use. Polymerization grade ethylene was used and further purified by passing it through a series of columns: 500 cc Oxyclear cylinder from Labclear (Oakland, Calif.) followed by a 500 cc column packed with dried 3 Å mole sieves purchased from Aldrich Chemical Company, and a 500 cc column packed with dried 5 Å mole sieves purchased from Aldrich Chemical Company. TnOAl (tri-n-octylaluminum, neat) was used as a 2 mmol/L solution in toluene.

Reactor Description and Preparation: Polymerizations were conducted in an inert atmosphere (N₂) drybox using autoclaves equipped with an external heater for temperature control, glass inserts (internal volume of reactor=22.5 mL), septum inlets, regulated supply of nitrogen, ethylene and hexene, and equipped with disposable PEEK mechanical stirrers (800 RPM). The autoclaves were prepared by purging with dry nitrogen prior to use.

Ethylene/1-hexene Copolymerization: The reactor was prepared as described above, and then purged with ethylene. Isohexane,1-hexene and TnOAl were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (85° C.) and charged with ethylene to process pressure (130 psig=896 kPa) while stirring at 800 RPM. The transition metal compound (100 μL of a 3 mg/mL toluene slurry, unless indicated otherwise) was added via syringe with the reactor at process conditions. TnOAl was used as 200 □L of a 20 mmol/L in isohexane solution. Ethylene was allowed to enter (through the use of computer controlled solenoid valves) the autoclaves during polymerization to maintain reactor gauge pressure (+/−2 psig). Reactor temperature was monitored and typically maintained within +/−1° C. Polymerizations were halted by addition of approximately 50 psi O₂/Ar (5 mole % O₂) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched after a predetermined cumulative amount of ethylene had been added or for a maximum of 45 minutes polymerization time. The final conversion (in psi) of ethylene added/consumed is reported in Table 1, in addition to the quench time for each run. The reactors were cooled and vented. The polymer was isolated after the solvent was removed in-vacuo. Yields reported include total weight of polymer and residual catalyst. Catalyst activity is reported as kilograms of polymer per mol transition metal compound per hour of reaction time (kg/mol·hr). Characterization data for polymers produced are shown in FIGS. 1 to 4.

TABLE 1 Ethylene Hexene Polymerization. Run Condition: Isohexane as Solvent, 85° C., 130 psi Ethylene Pressure, 30 μl of 1-hexene, 300 ppm hydrogen. Supported mol ratio of Final Ethylene Activity Mw Mw/ Catalyst Catalysts Uptake (psi) (kg/mol * h) (g/mol) Mn a-1 A/B = 5.8 55 28,092 161,000 3.6 b-1 A/C = 5.8 55 14,076 189,000 5.4 c-1 A/D = 3.2 55 13,705 204,000 6.3 d-1 A/E = 5.8 55 12,334 180,000 2.9

TABLE 2 Ethylene Hexene Polymerization. Run Condition: Isohexane as Solvent, 85° C., 130 psi Ethylene Pressure, 30 μl of 1-hexene, 0 ppm hydrogen. Supported Averaged Activity Catalyst Support (kg/mol * h) i-1 Fluorided silica-1 (dry-mix) 24371 i-2 Fluorided silica-2 (wet-mix) 21990 j-1 Fluorided silica-1 (dry-mix) 7481 j-2 Fluorided silica-2 (wet-mix) 9532

EXAMPLE 3 Polymerization of Ethylene and Hexene

Polymerization was performed in a gas-phase fluidized bed reactor with a 6″ body and a 10″ expanded section. Cycle and feed gases were fed into the reactor body through a perforated distributor plate, and the reactor was controlled at 300 psi and 70 mol % ethylene. Reactor temperature was maintained by heating the cycle gas. Supported catalyst was fed as a 10 wt % slurry in Sono Jell® from Sonneborn (Parsippany, N.J.). The slurry was thinned and delivered to the reactor by nitrogen and isopentane feeds in the cat probe. Products were collected from the reactor as necessary to maintain the desired bed weight. Average process conditions are listed in Tables 3 and 4.

TABLE 3 Average Process Conditions for Supported Catalysts e-1 and e-2. Supported Catalyst e-1* e-2 Catalyst Composition Catalyst A/ Catalyst A/ Catalyst B = 2.9 Catalyst B = 3 Support Fluoride silica-1 Fluoride silica-2 (dry-mix) (wet-mix) Temperature (° C.) 185 185 Pressure (psi) 300 300 Ethylene (mole %) 69.8 70.0 Hydrogen (ppm) 264 270 Hexene (mole %) 1.32 1.31 Bed Weight (g) 2000 2000 Residence Time (hr) 6.5 5.0 Cycle Gas Velocity (ft/s) 1.48 1.52 Production Rate (g/hr) 310 399 Activity (g_(poly)/g_(supported cat)) 1100 2260 Catalyst Slurry Feed (cc/hr) 3.2 2.0 MI I2.1 (g/10 min) 1.50 1.07 HLMI I21 (g/10 min) 34.04 26.15 MIR (I21/I2.1) 22.69 24.37 Density (g/cm³) 0.9156 0.9185 Bulk Density (g/cc) 0.2428 0.3344 N₂ Cat. Probe Feed (cc/min) 6000 6000 iC₅ Cat. Probe Feed (g/min) 1 1 *Values are averaged over the run including catalyst probe plugging issue. *No operability issue was encountered with supported catalyst e-2. Good activity (2260 g PE/g supported catalyst) was obtained. *Catalyst feed line was repeatedly plugged when running supported catalyst e-1.

TABLE 4 Average Process Conditions for the Supported Catalysts f-1 and f-2. Supported Catalyst h-1 h-2 Catalyst Composition Catalyst A/ Catalyst A/ Catalyst C = 2.8 Catalyst C = 3 Support Fluoride silica-1 Fluoride silica-2 (dry-mix) (wet-mix) Temperature (° C.) 185 185 Pressure (psi) 300 300 Ethylene (mole %) 70.0 70.0 Hydrogen (ppm) 180 180 Hexene (mole %) 2.71 2.14 Bed Weight (g) 2000 2000 Residence Time (hr) 4.8 4.8 Cycle Gas Velocity (ft/s) 1.53 1.52 Production Rate (g/hr) 414 416 Activity (g_(poly)/g_(supported cat)) 2380 2277 Catalyst Slurry Feed (cc/hr) 2.0 2.1 MI I2.1 (g/10 min) 1.07 0.98 HLMI I21 (g/10 min) 41.2 40.1 MIR (I21/I2.1) 38.4 40.9 Density (g/cm³) 0.9206 0.9174 Bulk Density (g/cc) 0.3872 0.3793 N₂ Cat. Probe Feed (cc/min) 6000 6000 iC₅ Cat. Probe Feed (g/min) 1 1

TABLE 5 Average Process Conditions for the Supported Catalysts e-2, f-1 and g-2. Supported Catalyst e-2 f-1 g-2 Catalyst Composition Catalyst A/ Catalyst A/ Catalyst A/ Catalyst Catalyst Catalyst B = 12 Support Fluoride Fluoride Fluoride silica-2 silica-1 silica-2 Temperature (° C.) 185 185 185 Pressure (psi) 300 300 300 Ethylene (mole %) 70.0 70.0 70.1 Hydrogen (ppm) 270 327 601 Hexene (mole %) 1.31 1.12 0.97 Bed Weight (g) 2000 2000 2000 Residence Time (hr) 5.0 4.6 Cycle Gas Velocity 1.52 1.62 1.49 Production Rate (g/hr) 399 454 431 Activity (g_(poly)/g_(supported) 2260 1870 2070 Catalyst Slurry Feed 2.0 2.8 2.4 MI I2.1 (g/10 min) 1.07 1.04 0.93 HLMI I21 (g/10 min) 26.15 32.71 60.36 MIR (I21/I2.1) 24.37 31.53 64.64 Density (g/cm³) 0.9185 0.917 0.9170 Bulk Density (g/cc) 0.3344 0.3444 0.3216 N₂ Cat. Probe Feed 6000 6000 6000 iC₅ Cat. Probe Feed 1 1

Melt index (MI) also referred to as 12, reported in g/10 min, is determined according to ASTM 1238, 190° C., 2.16 kg load.

High load melt index (HLMI) also referred to as 121, reported in g/10 min, is determined according to ASTM 1238, 190° C., 21.6 kg load.

Melt index ratio (MIR) is MI divided by HLMI is determined by ASTM 1238. Density is determined according to ASTM D 1505.

The MI, HLMI, MIR and density data in Tables 3, 4 and 5 are averaged numbers based on several measurements.

All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of”, “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa. Likewise, the terms “comprising,” “consisting essentially of,” “consisting of” also include the product of the combinations of elements listed after the term. 

1. A catalyst system comprising the reaction product of fluorided silica support, alkylalumoxane activator and at least two metallocene catalyst compounds, where the first metallocene is a bridged monocyclopentadienyl group 4 transition metal compound and the second metallocene is a biscyclopentadientyl group 4 transition metal compound where the fluorided silica support has not been calcined at a temperature of 400° C. or more.
 2. The catalyst system of claim 1, wherein the metallocenes are represented by the formula: T_(y)Cp_(m)MG_(n)X_(q) wherein each Cp is, independently, a cyclopentadienyl group which may be substituted or unsubstituted, M is a group 4 transition metal, G is a heteroatom group represented by the formula JR*_(z) where J is N, P, O or S, and R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms and z is 1 or 2, T is a bridging group, and y is 0 or 1, X is a leaving group, and m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal; wherein m=1, n=1 and y=1 in the first metallocene catalyst compound; and n=0 and m=2 in the second metallocene catalyst compound.
 3. The catalyst system of claim 2, wherein y is one in the second metallocene compound and at least one Cp in the second metallocene compound is not a substituted or unsubstituted indene group.
 4. The catalyst system of claim 2, wherein each Cp is a cyclopentadiene, indene or fluorene, which may be substituted or unsubstituted, each M is titanium, zirconium, or hafnium, and each X is, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.
 5. The catalyst system of claim 1, wherein the activator further comprises a non-coordinating anion activator.
 6. The catalyst system of claim 1, wherein the activator comprises methylalumoxane.
 7. The catalyst system of claim 1, wherein for the bridged monocyclopentadienyl transition metal compound m is one, n is one, J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.
 8. The catalyst system of claim 1, wherein the bridged monocyclopentadienyl transition metal compound comprises one or more of: dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl, dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl, dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride, μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M(R)₂; μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)₂; μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂; μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂; μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂; μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)₂; μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)₂; μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂; μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂; μ-(CH₃)₂Si(η⁵-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M(R)₂; where M is selected from a group consisting of Ti, Zr, and Hf and R is selected from halogen or C1 to C5 alkyl.
 9. The catalyst system of claim 1, wherein the second metallocene compound comprises one or more of: Bis(tetrahydroindenyl)Hf Me₂; Bis(1-butyl,3-methylcyclopentadienyl)ZrCl₂; Bis-(n-butylcyclopentadienyl)ZrCl₂; (Dimethylsilyl)₂O bis(indenyl)ZrCl₂; Dimethylsilyl(3-(3-methylbutyl)cyclopentadienyl)(2,3,4,5-tetramethylcyclopentadienyl)ZrCl₂; Dimethylsilylbis(tetrahydroindenyl)ZrCl₂; Dimethylsilyl-(3-phenyl-indenyl)(tetramethylcyclopentadienyl)ZrCl₂; Dimethylsilyl(3-neopentylcyclopentadienyl)(tetramethylcyclopentadienyl)HfCl₂; Tetramethyldisilylene bis(4-(3,5-di-tert-butylphenyl)-indenyl)ZrCl₂; Cyclopentadienyl(1,3-diphenylcyclopentadienyl)ZrCl₂; bis(cyclopentadienyl)zirconium dichloride; bis(pentamethylcyclopentadienyl)zirconium dichloride; bis(pentamethylcyclopentadienyl)zirconium dimethyl; is(pentamethylcyclopentadienyl)hafnium dichloride: bis(pentamethylcyclopentadienyl)zirconium dimethyl; bis(1-methyl-3-n-butylcyclopentadienyl)zixconium dichloride; bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl; bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride; bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl; bis(indenyl)zirconium dichloride; bis(indenyl)zirconium dimethyl; bis(tetrahydro-1-indenyl)zirconium dichloride; bis(tetrahydro-1-indenyl)zirconium dimethyl; dimethylsilylbis(tetrahydroindenyl)zirconium dichloride; dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl; dimethylsilylbis(indenyl)zirconium dichloride; dimethylsilyl(bisindenyl)zirconium dimethyl; dimethylsilylbis(cyclopentadienyl)zirconium dichloride; and dimethylsilylbis(cyclopentadienyl)zirconium dimethyl.
 10. The catalyst system of claim 1, wherein the first and second metallocene compounds comprise one or more of: SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and bis(1-Bu,3-Me-Cp) ZrCl₂; SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂) bis(indenyl)ZrCl₂; SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrCl₂; SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrMe₂; SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂and SiMe₂(3-neopentylCp)((Me₄Cp)HfCl₂; SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and SiMe₂(3-neopentylcyclopentadienyl)(Me₄Cp)HfMe₂; SiMe₂(Me₄Cp)(1-adamantylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂; and SiMe₂(Me₄Cp)(1-t-butylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂.
 11. The catalyst system of claim 1, wherein the flourided support has been calcined at a temperature of 100 to less than 400° C.
 12. A process to produce ethylene polymer comprising: i) contacting, in the gas phase or slurry phase, ethylene and, optionally C₃ to C₂₀ comonomer, with a catalyst system comprising a fluorided silica support, an alkylalumoxane activator, and at least two metallocene catalyst compounds, where the first metallocene is a bridged monocyclopentadienyl group 4 transition metal compound and the second metallocene is a biscyclopentadientyl group 4 transition metal compound, where the fluorided support has not been calcined at a temperature of 400° C. or more, and ii) obtaining an ethylene polymer comprising at least 50 mol % ethylene.
 13. The process of claim 12, wherein the ethylene polymer comprises ethylene and at least one C₃ to C₂₀ comonomer and has a bi-modal composition distribution.
 14. The process of claim 13, wherein the ethylene polymer has a multimodal molecular weight distribution as determined by Gel Permeation Chromotography.
 15. A method of preparing fluorided silica supported catalyst systems comprising combining a fluoride compound with a polar solvent, then combining with a slurry of non-polar solvent and silica support, removing the non-polar solvent, thereafter combining the calcined support with a second solvent, which may be the same as or different from the non-polar solvent, and two catalyst compounds and activator, wherein the fluorided support is calcined at a temperature from 100 to less than 400° C., before or after combination with the activator and/or catalyst compounds.
 16. The method of claim 15, wherein the ratio (by weight) of polar solvent to non-polar solvent is between 1:10 to 1:1000.
 17. The method of claim 16, wherein the polar solvent is water and non-polar solvent is toluene, pentane, hexane, benzene, or chloroform.
 18. The method of claim 16 where in the fluoride compound is one or more of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆, GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅, IF₇, NF₃, HF, BF₃, NHF₂ and NH₄HF₂.
 19. The method of claim 16, wherein the fluoride compound comprises ammonium hexafluorosilicate, ammonium tetrafluoroborate or a mixture thereof.
 20. The method of claim 12, wherein the activator comprises methylalumoxane.
 21. The method of claim 20, wherein the activator further comprises a non-coordinating anion activator.
 22. The method of claim 12, wherein the process occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time up to 300 minutes.
 23. The method of claim 12, wherein the comonomer is present and is selected from propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene or a mixtures thereof.
 24. The process of claim 12, wherein the fluorided supported catalyst system is prepared by the method comprising combining a fluoride compound with water, then combining with a slurry of non-polar solvent and support, removing the non-polar solvent, thereafter combining the calcined support with a second solvent, which may be the same as or different from the non-polar solvent, two catalyst compounds and activator, wherein the fluorided support is calcined at a temperature from 100 to less than 400° C., before or after combination with the activator and/or catalyst compounds.
 25. The method of claim 24 wherein the ratio (by weight) of water to non-polar solvent is between 1:10 to 1:1000; the non-polar solvent is toluene, pentane, hexane, benzene, or chloroform; and the fluoride compound is one or more of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆, GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅, IF, NF₃, HF, BF₃, NHF₂ and NH₄HF₂. 